CN107431130A - The manufacture method of photo-electric conversion element, solar cell and photo-electric conversion element - Google Patents
The manufacture method of photo-electric conversion element, solar cell and photo-electric conversion element Download PDFInfo
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- CN107431130A CN107431130A CN201680014566.7A CN201680014566A CN107431130A CN 107431130 A CN107431130 A CN 107431130A CN 201680014566 A CN201680014566 A CN 201680014566A CN 107431130 A CN107431130 A CN 107431130A
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- conversion element
- electric conversion
- compound
- atom
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The present invention provides a kind of photo-electric conversion element (10),Use the manufacture method of the solar cell and photo-electric conversion element (10) of the photo-electric conversion element,The photo-electric conversion element (10) is with the 1st electrode (1) with the photosensitive layer (13) comprising light absorber in conductive support (11) and 2nd electrode (2) opposed with the 1st electrode (1),Wherein,Light absorber includes the compound with specific perovskite type crystal structure,There is the compound represented with specific formula on the surface of the 1st electrode (1),In the manufacture method of the photo-electric conversion element (10),Make in conductive support with being contacted comprising 1st electrode (1) of the compound with specific perovskite type crystal structure as the photosensitive layer (13) of light absorber with containing the liquid of compound represented with following formula (AC).
Description
Technical field
The present invention relates to the manufacture method of a kind of photo-electric conversion element, solar cell and photo-electric conversion element.
Background technology
Photo-electric conversion element is used for various optical sensors, duplicator, solar cell etc..Solar cell is used as using non-
The battery of Depletion solar energy, expect that it is formal practical.Wherein, in recent years, by the change with perovskite type crystal structure
The solar cell that the metal halides such as compound (below, sometimes referred to as perovskite compound) are used as light absorber attracts attention.
Report has the achievement in research that higher photoelectric transformation efficiency can be realized in this solar cell.It is for example, non-
Recorded in patent document 1 by using thiophene or pyridine to CH3NH3PbI3―xClxThe crystal of the perovskite compound of expression
Surface carries out surface stabilizing treatment (passivation), power conversion efficiency (power conversion efficency)
It is improved.
Conventional art document
Patent document
Non-patent literature 1：ACS Nano, DOI：10.1021/nn5036476
The content of the invention
The invention technical task to be solved
Perovskite compound is used as in the solar cell of light absorber, except require higher initial performance (for example,
Short circuit current (referred to as electric current), open-circuit voltage, photoelectric transformation efficiency), also require through when after also suppress under initial performance
The durability of drop.But the stability of perovskite compound and insufficient.Perovskite compound is used as to the sun of light absorber
The initial performance of energy battery can over time pass through and decline.The solar cell that perovskite compound is used as to light absorber is firm
Exploitation without how long, therefore for battery performance, not yet sufficiently studied, inquired into.
Therefore, problem of the invention is to provide a kind of photo-electric conversion element that perovskite compound is used as to light absorber
And the photo-electric conversion element of excellent in te pins of durability and the solar cell using the photo-electric conversion element.Also, the problem of the present invention
It is to provide a kind of photoelectric conversion element for manufacturing and also playing excellent durability as light absorber even if by perovskite compound
The method of part.
For solving the means of technical task
The present inventor etc. has found the photo-electric conversion element and solar cell that perovskite compound is used as to light absorber
In, by setting specific compound on the surface of the photosensitive layer comprising perovskite compound, initial performance especially electric current can be obtained
Value is not easy the photo-electric conversion element declined and solar cell.The present invention be according to the opinion, further studied and
Complete.
That is, solves above-mentioned problem by the following method.
A kind of photo-electric conversion elements of the ＞ of ＜ 1, its with conductive support with the photosensitive layer comprising light absorber
The 1st electrode and the 2nd electrode with the 1st electrode contraposition, wherein,
Light absorber, which includes, possesses the cation with periodic table first family element or cationic organic group A, week
The cation of metallic atom M beyond phase table first family element and the calcium titanium of anionic property atom or atomic group X anion
The compound of ore deposit type crystal structure,
There is the compound represented with following formula (AC) on the surface of the 1st electrode.
[chemical formula 1]
In formula, ring AACRepresent heterocycle.Z represents sulphur atom or oxygen atom.nZRepresent more than 1 integer.A represents ＞ C=
CRY1RY2, ＞ C=S, ＞ C=O or ＞ C=NRY3。RY1And RY2Separately represent substituent.RY3Represent hydrogen atom or substitution
Base.nARepresent more than 0 integer.RACRepresent substituent.nRRepresent more than 0 integer.Wherein, Z is sulphur atom and nZFor 1 when, nR
Represent more than 1 integer.
Photo-electric conversion elements of the ＞ of ＜ 2 according to the ＞ of ＜ 1, wherein, RACFor halogen atom, the alkyl of carbon number more than 5
Or the group with halogen atom.
Photo-electric conversion elements of the ＞ of ＜ 3 according to the ＞ of ＜ 1 or the ＞ of ＜ 2, wherein, ring AACFor the virtue of 5 yuan of rings or 6 yuan of rings
Fragrant race's heterocycle.
Photo-electric conversion elements of the ＞ of ＜ 4 according to any one of the ＞ of the ＞ of ＜ 1 to ＜ 3, wherein, Z at least one is former for oxygen
Son.
Photo-electric conversion elements of the ＞ of ＜ 5 according to any one of the ＞ of the ＞ of ＜ 1 to ＜ 4, wherein, ring AACFor furan nucleus.
Photo-electric conversion elements of the ＞ of ＜ 6 according to any one of the ＞ of the ＞ of ＜ 1 to ＜ 5, wherein, there is perovskite
The compound of structure is the compound represented with following formula (I).
Formula (I)：AaMmXx
In formula, A represents periodic table first family element or the cationic organic group represented with following formula (1).M represents week
Metallic atom beyond phase table first family element.X represents anionic property atom or atomic group.A represents 1 or 2, m expression 1, a, m
And x meets a+2m=x.
Formula (1)：R1a-NH3
In formula, R1aRepresent substituent.
Photo-electric conversion elements of the ＞ of ＜ 7 according to the ＞ of ＜ 6, wherein, R1aFor alkyl, cycloalkyl, alkenyl, alkynyl, aryl,
Heteroaryl or the group that can be represented with following formula (2).
[chemical formula 2]
In formula, XaRepresent NR1c, oxygen atom or sulphur atom.R1bAnd R1cSeparately represent hydrogen atom or substituent.***
Expression is bonded with the nitrogen-atoms of formula (1).
Photo-electric conversion elements of the ＞ of ＜ 8 according to any one of the ＞ of the ＞ of ＜ 1 to ＜ 7, wherein, metallic atom is selected from bag
At least one kind of metallic atom in leaded and tin group.
Photo-electric conversion elements of the ＞ of ＜ 9 according to any one of the ＞ of the ＞ of ＜ 1 to ＜ 8, wherein, in the 1st electrode and the 2nd electricity
There is hole transmission layer between pole.
Photo-electric conversion elements of the ＞ of ＜ 10 according to any one of the ＞ of the ＞ of ＜ 1 to ＜ 9, wherein, in conductive support
There is porous layer between photosensitive layer.
A kind of solar cells of the ＞ of ＜ 11, it uses the photoelectric conversion element any one of the above-mentioned ＞ of the ＞ of ＜ 1 to ＜ 10
Part.
A kind of manufacture methods of photo-electric conversion element of the ＞ of ＜ 12, wherein, make in conductive support with comprising with
Metallic atom M beyond periodic table first family element or cationic organic group A cation, periodic table first family element
Cation and anionic property atom or atomic group X anion perovskite type crystal structure compound as light absorbs
1st electrode of the photosensitive layer of agent contacts with the liquid containing the compound represented with following formula (AC).
[chemical formula 3]
In formula, ring AACRepresent heterocycle.Z represents sulphur atom or oxygen atom.nZRepresent more than 1 integer.A represents ＞ C=
CRY1RY2, ＞ C=S, ＞ C=O or ＞ C=NRY3。RY1And RY2Separately represent substituent.RY3Represent hydrogen atom or substitution
Base.nARepresent more than 0 integer.RACRepresent substituent.nRRepresent more than 0 integer.Wherein, Z is sulphur atom, and nZFor 1 when,
nRRepresent more than 1 integer.
In this specification, on various mark, for the ease of understanding the chemical constitution of compound, sometimes also by a part
Labeled as rational formula.As it does so, in various, part-structure is referred to as (substitution) base, ion or atom etc., but in this specification, this
(substitution) base, ion or atom etc. are not only represented a bit, are also represented by forming (substitution) base or ion represented with above-mentioned formula sometimes
Element group or element.
In this specification, on compound (comprising complex compound, pigment) statement, except as compound itself with
Outside, the implication also comprising its salt, its ion.Moreover, recording substituted or unsubstituted compound on being not known, refer to lossless
The implication of the compound with any substituent is included in the range of target effect.This to substituent and linking group etc. (it is following,
Referred to as substituent etc.) it is also identical.
In this specification, multiple substituents etc. are provided when multiple substituents represented with special symbol etc. be present or simultaneously
When, unless otherwise specified, then each substituent etc. can be mutually identical also different.The regulation of this quantity to substituent etc. also phase
Together.Also, when multiple substituents etc. are close (when especially, adjacent), unless otherwise prescribed, these can be interconnected and form ring.
Also, ring such as alicyclic ring, aromatic ring, heterocycle can further condense and form condensed ring.
In this specification, the number range represented with "~" is denoted as lower limit and higher limit is included before being recorded in "~"
The scope of numerical value afterwards.
Invention effect
In the photo-electric conversion element and solar cell of the present invention, although perovskite compound is used as into light absorber,
Durability is still excellent.Also, according to the manufacture method of the photo-electric conversion element of the present invention, even if can manufacture perovskite chemical combination
Thing is used as light absorber, but the photo-electric conversion element that durability is still excellent.
On the above-mentioned and other feature and advantage of the present invention, the appropriate accompanying drawing for referring to apposition will more according to following records
Understand.
Brief description of the drawings
Fig. 1 is to schematically illustrate the excellent of the photo-electric conversion element of the present invention including the enlarged drawing of the circular portion in layer
Select the sectional view of mode.
Fig. 2 is the section view for the preferred embodiment with thicker photosensitive layer for schematically illustrating the photo-electric conversion element of the present invention
Figure.
Fig. 3 is to schematically illustrate the another of the photo-electric conversion element of the present invention including the enlarged drawing of the circular portion in layer
The sectional view of one preferred embodiment.
Fig. 4 is the sectional view for the another preferred embodiment for schematically illustrating the photo-electric conversion element of the present invention.
Fig. 5 is the sectional view for the another preferred embodiment for schematically illustrating the photo-electric conversion element of the present invention.
Fig. 6 is to schematically illustrate the photo-electric conversion element of the present invention including the enlarged drawing of the circular portion in layer
The sectional view of one preferred embodiment.
Embodiment
《Photo-electric conversion element》
The photo-electric conversion element of the present invention is with the 1st with the photosensitive layer comprising light absorber in conductive support
Electrode and the 2nd electrode with the 1st electrode contraposition.1st electrode has the compound represented with above-mentioned formula (AC) on its surface (sometimes
Referred to as compound AC).
In the present invention, it is to include with the surface of conductive support to connect and set to have photosensitive layer in conductive support
Put the mode of photosensitive layer and there is the implication of the mode of photosensitive layer via other layers in the surface of conductive support.
In the surface of conductive support via other layers and in the mode with photosensitive layer, as being arranged at conduction
Other layers between property supporting mass and photosensitive layer, as long as declining the battery performance of solar cell, are then not particularly limited.
For example, porous layer, barrier layer, electron transfer layer and hole transmission layer etc. can be enumerated.
In the present invention, as the mode via other layers in the surface of conductive support with photosensitive layer, example
Such as, photosensitive layer can be enumerated to be arranged to the mode (with reference to figure 1) of film-form etc. on the surface of porous layer, set on the surface of porous layer
Mode (with reference to figure 2 and Fig. 6) into thick film shape, on the surface on barrier layer it is arranged to the mode of film-form and on the surface on barrier layer
Be arranged to the mode (with reference to figure 3) of thick film shape, be arranged to film-form on the surface of electron transfer layer or the mode of thick film shape (reference
Fig. 4) and on the surface of hole transmission layer it is arranged to the mode of film-form or thick film shape (with reference to figure 5).Photosensitive layer can be set to line
Shape or dispersed, are preferably provided with film-like.
Also, in the present invention, " surface of the 1st electrode " represents to form the layer on the surface of the 1st electrode, for example, being arranged at the 1st
The surface of 2nd electrode side of the photosensitive layer of electrode.
In the present invention, " there is compound AC " represented on the surface of the 1st electrode in the surface of the 1st electrode or its presence nearby
Compound AC.The mode that compound AC be present is included by chemically bonding or physical interaction, and compound AC is in the 1st electricity
The surface bond of pole, adhesion, fixation, the mode for holding or adsorbing etc..For example, included in the surface of the 1st electrode, compound AC leads to
Cross covalent bond, ionic bond, mode, all modes for the mode physically adsorbed of coordinate bond bonding.In the present invention, compound
The surface how AC is actually present in the 1st electrode is unimportant, as long as compound be present near the surface of the 1st electrode or its
AC.Therefore, compound AC for example may be present in the hole of porous layer, and also a compound AC part can be introduced into sense
Photosphere.
Compound AC is simply by the presence of any shape that in the surface of the 1st electrode, can be membranaceous, wire and dispersed
State, and can also mix these state.In the present invention, for convenience of description, with compound AC on the surface of the 1st electrode
Possessed state independently, by the set for the compound AC having on the surface of the 1st electrode is referred to as compound AC layer (chemical combination
Nitride layer).Therefore, compound layer is not necessarily to be formed the layer or film on the surface as equably covered the 1st electrode.Therefore, each figure
In, in order to make it easy to understand, illustrating compound AC existence with stratiform, but equally it is not limited to this.
In the photo-electric conversion element of the present invention, the structure beyond structure specified in the present invention is not particularly limited, can
Using the known structure about photo-electric conversion element and solar cell.Each layer for forming the photo-electric conversion element of the present invention can
Designed according to purpose, such as be formed as individual layer and may be alternatively formed to multilayer.
Hereinafter, the preferred embodiment of the photo-electric conversion element of the present invention is illustrated.
In Fig. 1~Fig. 6, same-sign represents identical constitutive requirements (part).
In addition, Fig. 1, Fig. 2 and Fig. 6 emphasize to show to form the size of the particulate of porous layer 12.These particulates preferably with respect to
Conductive support 11 is in the horizontal direction and vertical direction fills (accumulation or adhesion) and forms porous structure.
In this specification, referred to as photo-electric conversion element 10 when, unless otherwise specified, then it represents that photo-electric conversion element 10A
~10F.This is also identical for system 100, the 1st electrode 1.Also, referred to as photosensitive layer 13 and during compound layer 5, unless otherwise
Indicate, then it represents that photosensitive layer 13A~13C or compound layer 5A~5C.Similarly, referred to as hole transmission layer 3 when, unless otherwise finger
It is bright, then it represents that hole transmission layer 3A and 3B.
As the preferred embodiment of the photo-electric conversion element of the present invention, such as the photo-electric conversion element shown in Fig. 1 can be enumerated
10A.System 100A shown in Fig. 1 is to be applied to make in external circuit 6 actuating mechanism M (such as electricity by photo-electric conversion element 10A
Dynamic motor) work battery use system.
Photo-electric conversion element 10A has the compound layer 5A (ginsengs on the 1st electrode 1A, the 1st electrode 1A photosensitive layer 13A
Examine Fig. 1 enlarging section A), the hole transmission layer 3A between the 2nd electrode 2 and the 1st electrode 1A and the 2nd electrode 2.
1st electrode 1A has the conductive support 11 comprising supporting mass 11a and transparency electrode 11b, porous layer 12 and more
Photosensitive layer 13A in aperture layer 12.Also, there is barrier layer 14 on transparency electrode 11b, formed with porous layer on barrier layer 14
12.In so photo-electric conversion element 10A with porous layer 12, photosensitive layer 13A surface area becomes big, it is inferred that being electric charge point
From and charge transfer effciency be improved.
Photo-electric conversion element 10B shown in Fig. 2 is to schematically illustrate the photo-electric conversion element set thicker shown in Fig. 1
The photo-electric conversion element of 10A photosensitive layer 13A preferred embodiment.In Fig. 2, photo-electric conversion element 10B compound layer and Fig. 1 institutes
The photo-electric conversion element 10A shown compound layer 5A is identical, therefore omits the enlarged drawing of compound layer.The photo-electric conversion element
In 10B, unfertile land is provided with hole transmission layer 3B.Photo-electric conversion element 10B and the photo-electric conversion element 10A phases shown in Fig. 1
Than, it is different on this point of photosensitive layer 13B and hole transmission layer 3B thickness, but be configured in addition and photo-electric conversion element
10A is identical.
Photo-electric conversion element 10C shown in Fig. 3 is other the preferred sides for schematically illustrating the photo-electric conversion element of the present invention
The photo-electric conversion element (the enlarging section A that compound layer 5B is shown in Fig. 3) of formula.Photoelectricity shown in photo-electric conversion element 10C and Fig. 2
Conversion element 10B is compared, different on this point of being not provided with porous layer 12, but is configured in addition and photo-electric conversion element
10B is identical.That is, in photo-electric conversion element 10C, photosensitive layer 13C is formed as thick film shape, compound layer 5B on the surface on barrier layer 14
It is formed at photosensitive layer 13C surface.In photo-electric conversion element 10C, hole transmission layer 3B can also be identical with hole transmission layer 3A
Ground is arranged to thicker.
Photo-electric conversion element 10D shown in Fig. 4 is the another preferred side for schematically illustrating the photo-electric conversion element of the present invention
The photo-electric conversion element of formula.In Fig. 4, photo-electric conversion element 10C's shown in photo-electric conversion element 10D compound layer and Fig. 3
Compound layer 5B is identical, therefore omits the enlarged drawing of compound layer.Opto-electronic conversion shown in photo-electric conversion element 10D and Fig. 3
Element 10C is compared, different barrier layer 14 is being provided with electron transfer layer 15 on this point, but is configured in addition and light
Electric transition element 10C is identical.The conductive supporting masses 11 of 1st electrode 1D and the electricity being sequentially formed in conductive support 11
Sub- transport layer 15 and photosensitive layer 13C.In photo-electric conversion element 10D, on this point of each layer can be formed with organic material compared with
It is preferred that.Thus, the productivity ratio of photo-electric conversion element is improved, and can realize slimming or flexibility.
Photo-electric conversion element 10E shown in Fig. 5 is the another preferred side for schematically illustrating the photo-electric conversion element of the present invention
The photo-electric conversion element of formula.In Fig. 5, in photo-electric conversion element 10E compound layer, on its surface formed with electron transfer layer 4
It is in addition, identical with the compound layer 5B of the photo-electric conversion element 10C shown in Fig. 3 to replace hole transmission layer 3B, therefore save
The slightly enlarged drawing of compound layer.System 100E comprising photo-electric conversion element 10E is electric to be applied to identically with system 100A
The system of pond purposes.
Photo-electric conversion element 10E is with the electronics between the 1st electrode 1E, the 2nd electrode 2 and the 1st electrode 1E and the 2nd electrode 2
Transport layer 4.The conductive supporting masses 11 of 1st electrode 1E and the hole transmission layer 16 being sequentially formed in conductive support 11
With photosensitive layer 13C.Photo-electric conversion element 10E can form each layer with organic material identically with photo-electric conversion element 10D
On this point more preferably.
Photo-electric conversion element 10F shown in Fig. 6 is the another preferred side for schematically illustrating the photo-electric conversion element of the present invention
The photo-electric conversion element (the enlarging section A that compound layer 5C is shown in Fig. 6) of formula.Photoelectricity shown in photo-electric conversion element 10F and Fig. 2
Conversion element 10B is compared, different on this point of being not provided with hole transmission layer 3B, in addition, is configured to and photoelectric conversion element
Part 10B is identical.
In the present invention, played a role as follows as solar cell using the system 100 of photo-electric conversion element 10.
That is, in photo-electric conversion element 10, transmission conductive supporting mass 11 or transmission the 2nd electrode 2 and be incident in photosensitive layer 13
Phot-luminescence absorbent.The light absorber being excited has high-energy electron, can release the electronics.Release high-energy electron
Light absorber turn into oxysome.
In photo-electric conversion element 10A~10D and 10F, from light absorber release electronics moved between light absorber and
Reach conductive support 11.The electronics of conductive support 11 is reached after external circuit 6 plays a role, by the 2nd electricity
Pole 2 (when hole transmission layer 3 be present, further via hole transmission layer 3) and return to photosensitive layer 13.By returning to photosensitive layer 13
Electronics, light absorber are reduced.
On the other hand, in photo-electric conversion element 10E, passed from the electronics that light absorber is released from photosensitive layer 13C by electronics
Defeated layer 4 and reach the 2nd electrode 2, external circuit 6 play a role after by conductive support 11 and return to photosensitive layer 13.
By returning to the electronics of photosensitive layer 13, light absorber is reduced.
In photo-electric conversion element 10, by be repeated this above-mentioned light absorber excite and the circulation of electron transfer,
System 100 plays a role as solar cell.
In photo-electric conversion element 10A~10D and 10F, electronics is from photosensitive layer 13 to the type of flow of conductive support 11
It is different according to the presence or absence of porous layer 12 and its species etc..In the photo-electric conversion element 10 of the present invention, electronics is produced in light absorbs
The electronics conduction migrated between agent.Therefore, when setting porous layer 12, porous layer 12 is in addition to conventional semiconductor, additionally it is possible to
Formed with insulator.When porous layer 12 is formed by semiconductor, electronics is also produced inside the semiconductive particles of porous layer 12 and half
The electronics conduction migrated between conductor particles.On the other hand, when porous layer 12 is formed by insulator, do not produce in porous layer 12
Electronics conducts.When porous layer 12 is formed by insulator, if using aluminum oxide (Al to insulator particulate2O3) particulate, then can obtain
Compare high electromotive force (Voc).
When the above-mentioned barrier layer 14 as other layers is formed by conductor or semiconductor, the electronics also produced in barrier layer 14 passes
Lead.
Also, electronics conduction is also produced in electron transfer layer 15.
The photo-electric conversion element and solar cell of the present invention is not limited to above-mentioned preferred embodiment, the structure of each mode
Etc. can be suitably combined between each mode without departing from the scope of spirit of the present invention.For example, such as photoelectric conversion element
Part 10F, additionally it is possible to which photo-electric conversion element 10C or 10D are set to be not provided with to hole transmission layer 3B structure.
In the present invention, on the material for photo-electric conversion element or solar cell and each part, except light absorber
And beyond compound AC, it can be prepared by a conventional method.On the photo-electric conversion element or the sun using perovskite compound
Energy battery, such as non-patent literature 1 can be referred to.
Also, to the material for DSSC and each part, it can be used as referring to.On using calcium
The photo-electric conversion element or solar cell of titanium ore compound, such as non-patent literature 1 can be referred to.It is also, quick on dyestuff
Change solar cell, such as 4,927, No. 721 Japanese Unexamined Patent Publication 2001-291534 publications, U.S. Patent No. explanations can be referred to
Book, No. 4,684,537 specifications of U.S. Patent No., No. 5,084,365 specifications of U.S. Patent No., U.S. Patent No. 5,350,
No. 644 specifications, No. 5,463,057 specifications of U.S. Patent No., U.S. Patent No. No. 5,525,440 specifications, Japanese Unexamined Patent Publications
Flat 7-249790 publications, Japanese Unexamined Patent Publication 2004-220974 publications, Japanese Unexamined Patent Publication 2008-135197 publications.
Hereinafter, the part and compound of the photo-electric conversion element and solar cell to being suitable for the present invention are said
It is bright.
The ＞ of the 1st electrodes of ＜ 1
1st electrode, 1 conductive supporting mass 11 and photosensitive layer 13, send out in photo-electric conversion element 10 as working electrode
The effect of waving.
As shown in Fig. 1~Fig. 6, the 1st electrode 1 preferably there is porous layer 12, barrier layer 14, electron transfer layer 15 and hole to pass
At least one layer of defeated layer 16.
From the aspect of short circuit is prevented, the 1st electrode 1 preferably at least has barrier layer 14, from the angle of efficiency of light absorption
And from the aspect of preventing short circuit, further preferably there is porous layer 12 and barrier layer 14.
Also, from the aspect of the raising, slimming or flexibility of the productivity ratio of photo-electric conversion element, the preferably the 1st electricity
Pole 1 has the electron transfer layer 15 or hole transmission layer 16 formed by organic material.
- conductive support 11-
Conductive support 11 is as long as there is electric conductivity and can support photosensitive layer 13 etc., then is not particularly limited.It is conductive
Property supporting mass 11 be preferably the structure that is formed by conductive material such as metal, or there is the supporting of glass or plastics
Body 11a and be formed at supporting mass 11a surface the transparency electrode 11b as conducting film structure.Conduction can be substantially ensured that
During the intensity of property supporting mass 11, supporting mass 11a is simultaneously nonessential.
Wherein, as shown in Fig. 1~Fig. 6, more preferably it is coated with conduction on the surface of glass or the supporting mass 11a of plastics
Property metal oxide carrys out film forming transparency electrode 11b conductive support 11.As the supporting mass 11a formed by plastics, such as
The transparent polymer film described in the paragraph 0153 of Japanese Unexamined Patent Publication 2001-291534 publications can be enumerated.As formation branch
Body 11a material is held, in addition to glass and plastics, additionally it is possible to using ceramic (Japanese Unexamined Patent Publication 2005-135902 publications), lead
Electrical resin (Japanese Unexamined Patent Publication 2001-160425 publications).It is especially excellent as metal oxide, preferably tin-oxide (TO)
Elect indium-tin-oxide (tin-doped indium oxide as；ITO the fluorine doped tin-oxides such as the tin oxide (FTO) of fluorine), are adulterated.On now
Every 1m of the coating weight of metal oxide, preferably supporting mass 11a2Surface area on be 0.1~100g.Use conductive support
When 11, preferably make light incident from supporting mass 11a sides.
It is preferred that conductive support 11 is actually transparent.In the present invention, " being actually transparent " represents light (wavelength 300
~1200nm) transmissivity be more than 10%, preferably more than 50%, especially preferably more than 80%.
Supporting mass 11a and the thickness of conductive support 11 are not particularly limited, and may be set to appropriate thickness.For example,
Preferably 0.01 μm~10mm, more preferably 0.1 μm~5mm, especially preferably 0.3 μm~4mm.
When setting transparency electrode 11b, transparency electrode 11b thickness is not particularly limited, for example, it is preferable to be 0.01~30 μ
M, more preferably 0.03~25 μm, especially preferably 0.05~20 μm.
Conductive support 11 or supporting mass 11a can have light regime function on surface.For example, can be in conductive support
11 or supporting mass 11a surface have described in Japanese Unexamined Patent Publication 2003-123859 publications be alternately laminated with high refraction film and
The antireflection film of the oxidation film of low-refraction, can also have the light guide work(described in Japanese Unexamined Patent Publication 2002-260746 publications
Energy.
- barrier layer 14-
In the present invention, such as photo-electric conversion element 10A~10C and 10F, the preferably surface in transparency electrode 11b, i.e. conductive
There is barrier layer 14 between property supporting mass 11 and porous layer 12, photosensitive layer 13 or hole transmission layer 3 etc..
In photo-electric conversion element and solar cell, if for example, photosensitive layer 13 or hole transmission layer 3 and transparency electrode 11b
Deng electrical connection, then reverse current can be produced.Barrier layer 14 plays the function of preventing the reverse current.Barrier layer 14 is also referred to anti-short
Road floor.
Barrier layer 14 can also be made to be played a role as the support for holding light absorber.
The barrier layer 14 can also be set when photo-electric conversion element has electron transfer layer.For example, photo-electric conversion element 10D
In the case of, it may be disposed between conductive support 11 and electron transfer layer 15, can in the case of photo-electric conversion element 10E
It is arranged between the 2nd electrode 2 and electron transfer layer 4.
As long as the material of above-mentioned function can be played by forming the material on barrier layer 14, then it is not particularly limited, is preferably
Make the material of visible transmission and relative to the material of the insulating properties such as conductive support 11 (transparency electrode 11b).Specifically,
Refer to " relative to the insulating properties material of conductive support 11 (transparency electrode 11b) ", the energy level of conduction band is to form electric conductivity branch
More than the energy level for holding the conduction band of the material (metal oxide for forming transparency electrode 11b) of body 11, and form the material of porous layer 12
Compound (n-type semiconductor compound) below the energy level of the conduction band of material or the ground state of light absorber.
Silica, magnesia, aluminum oxide, calcium carbonate, polyvinyl alcohol, poly- ammonia can for example be enumerated by forming the material on barrier layer 14
Carbamate etc..And it is possible to be typically used for the material of photoelectric conversion material, for example, can also enumerate titanium oxide, tin oxide,
Zinc oxide, niobium oxide, tungsten oxide etc..Wherein, preferably titanium oxide, tin oxide, magnesia, aluminum oxide etc..
The thickness on barrier layer 14 is preferably 0.001~10 μm, more preferably 0.005~1 μm, especially preferably 0.01
~0.1 μm.
In the present invention, the thickness of each layer can observe photoelectric conversion element by using scanning electron microscope (SEM) etc.
The section of part 10 is measured.
- porous layer 12-
In the present invention, such as photo-electric conversion element 10A, 10B and 10F, there is porous layer 12 preferably on transparency electrode 11b.
During with barrier layer 14, preferably porous layer 12 is formed on barrier layer 14.
Porous layer 12 is the layer to be played a role as the support that photosensitive layer 13 is held on surface.In solar cell, in order to
Efficiency of light absorption is improved, the surface area for receiving the parts of light such as sunshine is preferably at least increased, preferably increases whole porous layer 12
Surface area.
Porous layer 12 is preferably punctulate micro- by forming the tool that the particulate of the material of porous layer 12 is accumulated or adhesion forms
Granulosa.Porous layer 12 can be the particulate layer formed by particulate of more than two kinds accumulation.If porous layer 12 is the punctulate particulate of tool
Layer, then it can increase the load amount of holding (adsorbance) of light absorber.
When increasing the surface area of porous layer 12, the surface area for each particulate for forming porous layer 12 is preferably increased.The present invention
In, in the state of the particulate for forming porous layer 12 is applied is located at the grade of conductive support 11, the surface area of the particulate relative to
Projected area, preferably more than 10 times, more preferably more than 100 times.There is no particular restriction for the upper limit, usually 5000 times of left sides
It is right.On the particle diameter for the particulate for forming porous layer 12, in the average grain diameter using the diameter that projected area is scaled to bowlder, make
It it is preferably 0.001~1 μm for 1 particle.When forming porous layer 12 using the dispersion of particulate, the above-mentioned average grain diameter of particulate is made
For the average grain diameter of dispersion, preferably 0.01~100 μm.
Material for forming porous layer 12, is not particularly limited on electric conductivity, can be the insulator (material of insulating properties
Material) can also be electric conductivity material or semiconductor (material of semiconduction).
As formed porous layer 12 material, for example, can use metal chalkogenide (such as oxide, sulfide,
Selenides etc.), have perovskite type crystal structure compound (be used as light absorber perovskite compound except.), silicon
Oxide (for example, silica, zeolite) or CNT (including carbon nanocoils and carbon nano rod etc.).
As the chalkogenide of metal, be not particularly limited, preferably enumerate titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium,
Yttrium, lanthanum, vanadium, niobium, each oxide of aluminium or tantalum, cadmium sulfide, cadmium selenide etc.., can as the crystal structure of the chalkogenide of metal
Enumerate Detitanium-ore-type, brookite type or rutile-type, preferably Detitanium-ore-type, brookite type.
As the compound with perovskite type crystal structure, it is not particularly limited, transition metal oxide etc. can be enumerated.
For example, strontium titanates, calcium titanate, barium titanate, lead titanates, barium zirconate, barium stannate, lead zirconates, strontium zirconate, tantalic acid strontium, potassium niobate, iron
Sour bismuth, barium strontium titanate, barium titanate lanthanum, calcium titanate, sodium titanate, bismuth titanates.Wherein, preferably strontium titanates, calcium titanate etc..
CNT has the shape that carbon film (graphene film) is rolled into tubular.CNT is categorized as 1 graphene film
Be rolled into cylindrical shape single-layer carbon nano-tube (SWCNT), 2 graphene films be rolled into concentric circles 2 layers of CNT (DWCNT),
Multiple graphene films are rolled into the multilayer carbon nanotube (MWCNT) of concentric circles.As porous layer 12, especially can not limitedly make
With any CNT.
Formed in the material of porous layer 12, preferably the oxide or CNT of titanium, tin, zinc, zirconium, aluminium or silicon, entered
One step is preferably titanium oxide or aluminum oxide.
As long as chalkogenide of the porous layer 12 by metal, the compound with perovskite type crystal structure, the oxide of silicon
And at least one kind of formation in CNT, it can also be formed by a variety of.
The thickness of porous layer 12 is not particularly limited, generally in 0.05~100 μm of scope, during as solar cell,
Preferably 0.1~50 μm, more preferably 0.2~30 μm.
- electron transfer layer 15-
In the present invention, such as photo-electric conversion element 10D, preferably there is electron transfer layer 15 on transparency electrode 11b surface.
Electron transfer layer 15 has the function that the caused electronics in photosensitive layer 13 is transmitted to conductive support 11.Electronics
Transport layer 15 is formed by the electron transport material that can play the function.As electron transport material, it is not particularly limited, preferably
For organic material (Organic Electron Transport Material).As Organic Electron Transport Material, [6,6]-phenyl-C61- butyric acid first can be enumerated
Ester (PC61The compound such as fullerene compound, tetracarboxylic acid diimide (PTCDI) such as BM), can additionally enumerate four cyano
The low molecular compounds or high-molecular compound etc. such as paraquinones bismethane (TCNQ).
The thickness of electron transfer layer 15 is not particularly limited, preferably 0.001~10 μm, more preferably 0.01~1 μm.
- hole transmission layer 16-
In the present invention, such as photo-electric conversion element 10E, preferably there is hole transmission layer 16 on transparency electrode 11b surface.
Hole transmission layer 16 is identical with hole transmission layer 3 described later in addition to the position difference formed.
- photosensitive layer (light absorbing layer) 13-
Photosensitive layer 13 is preferably disposed on porous layer 12 (photo-electric conversion element 10A, 10B and 10F), (photoelectricity turns on barrier layer 14
Change element 10C), each layer of electron transfer layer 15 (photo-electric conversion element 10D) or hole transmission layer 16 (photo-electric conversion element 10E)
Surface (comprising set photosensitive layer 13 surface for it is concavo-convex when recess inner surface.).
In the present invention, as long as light absorber contains at least one kind of specific perovskite compound described later, it can also contain 2
The perovskite compound of the kind above.Also, light absorber can be together included beyond perovskite compound with perovskite compound
Light absorber.As the light absorber beyond perovskite compound, such as metal complex dyes and organic dyestuff can be enumerated.This
When, the ratio between perovskite compound and light absorber beyond it is not particularly limited.
Photosensitive layer 13 can be the stacking that individual layer can also be more than 2 layers.Photosensitive layer 13 is more than 2 layers of stepped construction
When, the stepped construction formed comprising mutually different light absorber can be laminated, and can also be photosensitive layer and photosensitive layer it
Between have the intermediate layer comprising hole mobile material stepped construction.
The mode with photosensitive layer 13 is as described above in conductive support 11.Photosensitive layer 13 is preferably disposed on above-mentioned each
The surface of layer, with the electron stream that toilet excites to the electrode 2 of conductive support 11 or the 2nd.Now, photosensitive layer 13 may be disposed at
The whole surface of each layer is stated, may also set up the part in the surface.
Photosensitive layer 13 has the compound represented with following formula (AC) on its surface.Compound AC is present in the side on surface
Formula is as described above.
The thickness of photosensitive layer 13 is suitably set according to the mode for having photosensitive layer 13 in conductive support 11, has no spy
Do not limit.For example, it is preferable to be 0.001~100 μm, more preferably 0.01~10 μm, especially preferably 0.01~5 μm.
During with porous layer 12, total thickness with the thickness of porous layer 12 is preferably more than 0.01 μm, more preferably
More than 0.05 μm, more preferably more than 0.1 μm, especially preferably more than 0.3 μm.Also, total thickness is preferably 100 μm
Hereinafter, more preferably less than 50 μm, more preferably less than 30 μm.Total thickness can be set to the model of appropriately combined above-mentioned value
Enclose.For example, it is preferable to be 0.01~100 μm, more preferably 0.05~50 μm, especially preferably 0.1~30 μm.
When there is porous layer 12 and hole transmission layer 3 in photo-electric conversion element 10, porous layer 12, photosensitive layer 13, compound
Layer 5 and total thickness of hole transmission layer 3 are not particularly limited, for example, it is preferable to be 0.01~200 μm, more preferably 0.05~
50 μm, more preferably 0.1~30 μm.
In the present invention, when photosensitive layer is arranged into thick film shape (photosensitive layer 13B and 13C), the light included in the photosensitive layer is inhaled
Agent is received also to play a role as hole mobile material sometimes.
The usage amount of perovskite compound is preferably at least one of amount on the surface for covering the 1st electrode 1, more preferably
Cover the amount of whole surface.
(light absorber of photosensitive layer)
Photosensitive layer 13 includes as light absorber has " periodic table first family element or cationic organic group A ", " week
Metallic atom M " and " anionic property atom or atomic group X " perovskite compound beyond phase table first family element.
Periodic table first family element or cationic organic group A, the metallic atom M and anionic property of perovskite compound
Atom or atomic group X are in perovskite type crystal structure, respectively as cation (for convenience of description, sometimes referred to as cation
A), metal cation (for convenience of description, sometimes referred to as cation M) and anion (for convenience of description, it is sometimes referred to as cloudy from
Sub- X) each composition ion and exist.
In the present invention, cationic organic group refers to the property for turning into cation in perovskite type crystal structure
Organic group, anionic property atom or atomic group refer to the property in perovskite type crystal structure as anion
Atom or atomic group.
In the perovskite compound used in the present invention, cation A be the cation comprising periodic table first family element or
Cationic organic group A organic cation.Cation A is preferably organic cation.
The cation of periodic table first family element is not particularly limited, for example, can enumerate lithium (Li), sodium (Na), potassium (K) or
Cation (the Li of each element of caesium (Cs)+、Na+、K+、Cs+), the especially preferably cation (Cs of caesium+)。
As long as the cation of organic group of the organic cation with above-mentioned property, then be not particularly limited, further
The organic cation of the cationic organic group preferably represented with following formula (1).
Formula (1)：R1a-NH3
In formula, R1aRepresent substituent.R1aAs long as organic group, be then not particularly limited, preferably alkyl, cycloalkyl,
Alkenyl, alkynyl, aryl, heteroaryl or the group that can be represented with following formula (2).Wherein, more preferably alkyl, can be with following
The group that formula (2) represents.
[chemical formula 4]
In formula, XaRepresent NR1c, oxygen atom or sulphur atom.R1bAnd R1cSeparately represent hydrogen atom or substituent.***
Expression is bonded with the nitrogen-atoms of formula (1).
In the present invention, cationic organic group A organic cation is preferably comprising the R in above-mentioned formula (1)1aWith NH3
It is bonded the ammonium cation organic group A formed organoammonium cations (R1a-NH3 +).The desirable resonance knot of the organoammonium cations
During structure, organic cation is in addition to organoammonium cations, the also cation comprising resonant structure.For example, can be with above-mentioned formula
(2) in the group represented, XaFor NH (R1cFor hydrogen atom) when, organic cation is except the group that can be represented with above-mentioned formula (2)
With NH3It is bonded beyond the organoammonium cations of the ammonium cation organic group formed, further comprises as the organoammonium cations
One of resonant structure organic amidine cation.As organic amidine cation comprising amidine cationic organic group, can enumerate
With following formula (Aam) represent cation., for convenience of description, sometimes will be with following formula (A in this specificationam) represent sun
Ion is labeled as " R1bC (=NH)-NH3”。
[chemical formula 5]
Alkyl is preferably the alkyl that carbon number is 1~18, more preferably 1~6 alkyl, and more preferably 1~3
Alkyl.For example, methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, amyl group or hexyl etc. can be enumerated.
Cycloalkyl is preferably the cycloalkyl that carbon number is 3~8, for example, cyclopropyl, cyclopenta or cyclohexyl can be enumerated
Deng.
Alkenyl be preferably carbon number be 2~18 alkenyl, more preferably 2~6 alkenyl.For example, can enumerate vinyl,
Pi-allyl, cyclobutenyl or hexenyl etc..
Alkynyl be preferably carbon number be 2~18 alkynyl, more preferably 2~4 alkynyl.For example, can enumerate acetenyl,
Butynyl or hexin base etc..
Aryl is preferably the aryl of carbon number 6~14, for example, the more preferably aryl of carbon number 6~12, can be enumerated
Phenyl.
Heteroaryl is included only comprising the group of heteroaromatic and for example fragrant comprising other rings are condensed to heteroaromatic
The group of the annelated heterocycles of ring, aliphatic ring or heterocycle.
Hetero atom, preferably nitrogen-atoms, oxygen atom, sulphur atom are formed as the ring for forming heteroaromatic.Also, as
The ring element number of heteroaromatic, preferably 3~8 yuan of rings, more preferably 5 yuan of rings or 6 yuan of rings.
The condensation heterocycle of heteroaromatic as the heteroaromatic of 5 yuan of rings and comprising 5 yuan of rings, for example, pyrrole can be enumerated
Cough up ring, imidazole ring, pyrazole ring, oxazole rings, thiazole ring, triazole ring, furan nucleus, thiphene ring, benzimidazole ring, benzoxazole ring,
Benzothiazole ring, indole ring and indazole ring.Also, heteroaromatic as 6 yuan of rings and the heteroaromatic for including 6 yuan of rings
Condensation heterocycle, for example, each ring group of pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring and quinazoline ring can be enumerated.
Can be with group that formula (2) represents, XaRepresent NR1c, oxygen atom or sulphur atom, preferably NR1c.Wherein, R1cTable
Show hydrogen atom or substituent, preferably hydrogen atom, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl, more preferably
Hydrogen atom.
R1bRepresent hydrogen atom or substituent, preferably hydrogen atom.R can be adopted as1bSubstituent can enumerate amino, alkyl,
Cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.
R1bAnd R1cThe implication of desirable alkyl, cycloalkyl, alkenyl, alkynyl, aryl and heteroaryl and above-mentioned R respectively1aIt is each
Base is identical, and preferred group is also identical.
As the group that can be represented with formula (2), for example, (thio) acyl group, (thio) carbamyl, imino group can be enumerated
Or amidino groups.
(thio) acyl group includes acyl group and Thioacyl.Acyl group is preferably the acyl group that total carbon atom number is 1~7, for example, can
Enumerate formoxyl, acetyl group (CH3C (=O) -), propiono, caproyl etc..Thioacyl is preferably that total carbon atom number is 1~7
Thioacyl, for example, thioformyl, ethanethioyl (CH3C (=S) -), thiopropionyl etc..
(thio) carbamyl includes carbamoyl (H2NC (=O) -) and thiocarbamoyl (H2NC (=S) -).
Imino group is with R1b- C (=NR1cThe group for)-represent, R1bAnd R1cHydrogen atom or alkyl are respectively preferably, more preferably
The implication of alkyl and above-mentioned R1aAlkyl it is identical.For example, imines formoxyl (HC (=NH) -), imino acetyl (CH can be enumerated3C
(=NH) -), imines propiono (CH3CH2C (=NH) -) etc..Wherein, preferably imines formoxyl.
Amidino groups as the group that can be represented with formula (2) has the R of above-mentioned imino group1bFor amino and R1cFor hydrogen atom
Structure (- C (=NH) NH2)。
R can be adopted as1aAlkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl and can be represented with above-mentioned formula (2)
Group can have substituent.As R1aThe substituent that can have, is not particularly limited, for example, can enumerate alkyl, cycloalkyl,
Alkenyl, alkynyl, aryl, heterocyclic radical, alkoxy, alkylthio group, amino, alkyl amino, arylamino, acyl group, alkyl carbonyl oxy, virtue
Epoxide, alkoxy carbonyl group, aryloxy carbonyl, acylamino-, sulfoamido, carbamyl, sulfamoyl, halogen atom, cyano group, hydroxyl or carboxylic
Base.R1aEach substituent that can have can be further substituted with a substituent.
In the perovskite compound used in the present invention, as long as beyond metal cation M periodic table first family elements
The cation of the metallic atom of metallic atom M cation and desirable perovskite type crystal structure, then be not particularly limited.As
This metallic atom, for example, calcium (Ca), strontium (Sr), cadmium (Cd), copper (Cu), nickel (Ni), manganese (Mn), iron (Fe), cobalt can be enumerated
(Co), the metal raw such as palladium (Pd), germanium (Ge), tin (Sn), lead (Pb), ytterbium (Yb), europium (Eu), indium (In), titanium (Ti), bismuth (Bi)
Son.Wherein, metallic atom M is preferably the cation of divalent, is more preferably selected from the lead cation (Pb comprising divalent2+), the copper of divalent
Cation (Cu2+), the germanium cation (Ge of divalent2+) and divalent tin cation (Sn2+) group in it is at least one kind of, further preferably
For Pb2+Or Sn2+, especially preferably Pb2+.M can be a kind of metallic atom or metallic atom of more than two kinds.2 kinds with
On metallic atom when, preferably this 2 kinds of Pb atoms and Sn atoms.The ratio of metallic atom now is not particularly limited.
In the perovskite compound used in the present invention, anion X represent anionic property atom or atomic group X it is cloudy from
Son.The anion can enumerate the anion or NCS of halogen atom-、NCO-、HO-、NO3 -、CH3COO-Or HCOO-Each atomic group
Anion.Wherein, the more preferably anion of halogen atom.As halogen atom, for example, fluorine atom, chlorine atom, bromine can be enumerated
Atom and iodine atom etc..
Anion X can be the anion of a kind of anionic property atom or atomic group or anion of more than two kinds
The anion of property atom or atomic group.For the anion of a kind of anionic property atom or atomic group when, preferably iodine atom it is cloudy from
Son.On the other hand, for the anion of anionic property atom of more than two kinds or atomic group when, preferably 2 kinds of halogen atoms it is cloudy from
Son, the especially anion of the anion of chlorine atom and iodine atom.The ratio of anion of more than two kinds is not particularly limited.
The perovskite compound used in the present invention possesses with above-mentioned each perovskite type crystal structure for forming ion, excellent
Elect the perovskite compound represented with following formula (I) as.
Formula (I)：AaMmXx
In formula, A represents periodic table first family element or cationic organic group.M represent periodic table first family element with
Outer metallic atom.X represents anionic property atom or atomic group.
A represents 1 or 2, m expression 1, and a, m and x meet a+2m=x.
In formula (I), periodic table first family element or cationic organic group A form the above-mentioned of perovskite type crystal structure
Cation A.Therefore, as long as periodic table first family element and cationic organic group A can turn into above-mentioned cation A and structure
Into the element or group of perovskite type crystal structure, then it is not particularly limited.Periodic table first family element or cationic are organic
Group A implication is identical with above-mentioned the periodic table first family element or cationic organic group that illustrate in above-mentioned cation A, excellent
Select group also identical.
Metallic atom M is the metallic atom for the above-mentioned metal cation M to form perovskite type crystal structure.Therefore, metal
As long as the atom beyond atom M periodic table first family elements, and above-mentioned metal cation M can be turned into and form Ca-Ti ore type
The atom of crystal structure, then be not particularly limited.Metallic atom M implication and the above-mentioned gold illustrated in above-mentioned metal cation M
Category atom is identical, and preferred group is also identical.
The above-mentioned anion X of anionic property atom or atomic group X-shaped into perovskite type crystal structure.Therefore, anionic property
As long as atom or atomic group X can turn into above-mentioned anion X and form the atom or atomic group of perovskite type crystal structure, then
It is not particularly limited.Anionic property atom or atomic group X implication and the anionic property atom or original illustrated in above-mentioned anion X
Son group is identical, and preferred group is also identical.
On the perovskite compound represented with formula (I), when a is 1, for the perovskite chemical combination represented with following formula (I-1)
Thing, when a is 2, for the perovskite compound represented with following formula (I-2).
Formula (I-1)：AMX3
Formula (I-2)：A2MX4
In formula (I-1) and formula (I-2), A represents periodic table first family element or cationic organic group, its implication with it is upper
State that the A of formula (I) is identical, and preferred group is also identical.
M represents the metallic atom beyond periodic table first family element, and its implication is identical with the M of above-mentioned formula (I), preferred group
Also it is identical.
X represents anionic property atom or atomic group, and its implication is identical with the X of above-mentioned formula (I), and preferred group is also identical.
The perovskite compound used in the present invention can be the compound represented with formula (I-1) and be represented with formula (I-2)
Compound in any one or their mixture.Therefore, in the present invention, inhaled in perovskite compound as light
Receive agent exist it is at least one kind of, without according to composition formula, molecular formula and crystal structure etc., it is strictly which kind of clearly to distinguish
Compound.
Hereinafter, the concrete example for the perovskite compound that can be used in the present invention is illustrated, but the present invention is not limited to this.
In following, it is divided into and is recorded with the compound that formula (I-1) represents with the compound that is represented with formula (I-2).Wherein, even as
The compound represented with formula (I-1) is come the compound that illustrates, according to synthesis condition etc., the change for existing to represent with formula (I-2)
The situation of compound, also, the mixing for turning into the compound represented with formula (I-1) and the compound represented with formula (I-2) also be present
The situation of thing.Similarly, even as the compound represented with formula (I-2) come the compound illustrated, there is also as with formula
(I-1) situation of the compound represented, also, also have what is turned into the compound represented with formula (I-1) and represented with formula (I-2)
The situation of the mixture of compound.
As the concrete example of the compound represented with formula (I-1), for example, CH can be enumerated3NH3PbCl3、CH3NH3PbBr3、
CH3NH3PbI3、CH3NH3PbBrI2、CH3NH3PbBr2I、CH3NH3SnBr3、CH3NH3SnI3、CH3NH3GeCl3, CH (=NH)
NH3PbI3、CsSnI3CsGeI3。
As the concrete example of the compound represented with formula (I-2), for example, (C can be enumerated2H5NH3)2PbI4、(C10H21NH3)2PbI4、(CH2=CHNH3)2PbI4、(CH≡CNH3)2PbI4、(n-C3H7NH3)2PbI4、(n-C4H9NH3)2PbI4、(C6H5NH3)2PbI4、(C6H5CH2CH2NH3)2PbI4、(C6H3F2NH3)2PbI4、(C6F5NH3)2PbI4、(C4H3SNH3)2PbI4、(CH3NH3)2CuCl4、(C4H9NH3)2GeI4、(C3H7NH3)2FeBr4.Wherein, (C4H3SNH3)2PbI4In C4H3SNH3For aminothiophene.
Perovskite compound can be by the compound represented with following formula (II) and the compound represented with following formula (III)
Synthesis.
Formula (II)：AX
Formula (III)：MX2
In formula (II), A represents periodic table first family element or cationic organic group, the A phases of its implication and formula (I)
Together, preferred group is also identical.In formula (II), X represents anionic property atom or atomic group, and its implication is identical with the X of formula (I), excellent
Select group also identical.
In formula (III), M represents the metallic atom beyond periodic table first family element, and its implication is identical with the M of formula (I), excellent
Select group also identical.In formula (III), X represents anionic property atom or atomic group, and its implication is identical with the X of formula (I), preferably base
Group is also identical.
On the synthetic method of perovskite compound, for example, the method described in non-patent literature 1 can be enumerated.Also, also
Akihiro Kojima, Kenjiro Teshima, Yasuo Shirai, and Tsutomu Miyasaka can be enumerated,
“Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic
Cells ", J.Am.Chem.Soc., 2009,131 (17), the method described in p6050-6051.
As long as the usage amount of light absorber covers at least one of amount on the surface of the 1st electrode 1, preferably cover
The amount of lid whole surface.
In photosensitive layer 13, the content of perovskite compound is usually 1~100 mass %.
- compound layer 5-
In the present invention, the compound represented with formula (AC) is present in the surface of the 1st electrode." have on the surface of the 1st electrode
Compound AC " mode and state is as described above.In the photo-electric conversion element of the present invention, hole preferably is set on the 1st electrode 1
Transmitting layer 3 or electron transfer layer 4.Now, compound layer 5 is intervened in the surface of the 1st electrode 1 and the layer being arranged on the 1st electrode 1
Between.
Compound AC is simply by the presence of in the surface of the 1st electrode.Compound AC can be confirmed as follows to whether there is in the 1st
The surface of electrode.That is, the surface of the 1st electrode of abundant area is cleaned with the organic solvent or water for being capable of dissolved compound AC.Root
According to needing that the filtrate for filtering obtained cleaning fluid is concentrated and purified, pass through gel permeation chromatography (GPC), efficient liquid
Phase chromatography (HPLC) or each magnetic resonance optical spectroscopy (NMR) are analyzed.The change on surface thereby, it is possible to confirm the 1st electrode
The presence or absence of compound AC, and its amount can be quantified.
On the amount for the compound AC for being present in surface, as long as the effect of the present invention can be played, then special limit is had no
It is fixed.As long as example, it can preferably make itself and the 1st electricity by making inclusion compound AC liquid be contacted with the surface of the 1st electrode
The amount that the whole surface of pole contacts to be arranged on the 1st electrode.Now, amount can be according to inclusion compound AC
Liquid concentration, make surface area etc. that it is contacted to change.As compound AC amount, though it is indefinite, if enumerating
One example, then for example, 0.1mg/m2~100g/m2.But also 1mg/m can be enumerated2~1g/m2。
In the present invention, consider from viewpoint for preventing reversed charge movement etc., the electrode of preferred compound AC uniform folds the 1st
Surface.
If having compound AC on the surface of the 1st electrode, the durability of photo-electric conversion element and solar cell is excellent
It is different.Though its detailed content is still not clear, infer as follows.That is, if there is compound AC on the surface of the 1st electrode, can carry
Compatibility between high 1st electrode and the layer (hole transmission layer, electron transfer layer or the 2nd electrode etc.) being formed on the 1st electrode
Or interaction etc..Especially, there is at least one of sulphur atom and oxygen atom as in the heterocycle of ring atom, such as
Pyridine, excellent spy is played in terms of the less aspect of influence burst apart or deformed or hydrophobicity to the crystal structure of perovskite
Property, can effectively suppress from inversion electron from the 1st electrode to the layer being arranged on the 1st electrode movement (photo-electric conversion element 10A~
10D, 10F) or from the layer being arranged on the 1st electrode to the reverse hole of the 1st electrode movement (photo-electric conversion element 10E).Also,
Heterocycle is from the beginning without prejudice to the electric charge transmission needed for surface (interface) script of the 1st electrode.By these, the 1st electrode with
Adhesiveness between the layer being formed on the 1st electrode is improved, and is produced electric charge rapidly along prescribed direction and is moved (electronics movement),
Further, it is possible to prevent the exception of bed boundary or the caused deterioration (decomposition of perovskite compound) of moisture absorption.Think thus, even in
Through when after can also suppress the decline of electric current, can also then suppress the decline of photoelectric transformation efficiency.
Think compound AC as substituent RACWith halogen atom, the alkyl of carbon number more than 5 or with halogen atom
During the hydrophobic group of group etc., the effect above can be improved further.
There is at least one kind of compound AC on the surface of the 1st electrode, can also have a variety of.
Compound AC is the compound represented with following formula (AC).
[chemical formula 6]
In formula, ring AACRepresent heterocycle.Z represents sulphur atom or oxygen atom.nZRepresent more than 1 integer.A represents ＞ C=
CRY1RY2, ＞ C=S, ＞ C=O or ＞ C=NRY3。RY1And RY2Separately represent substituent.RY3Represent hydrogen atom or substitution
Base.nARepresent more than 0 integer.RACRepresent substituent.nRRepresent more than 0 integer.Wherein, Z is sulphur atom, and nZFor 1 when,
nRRepresent more than 1 integer.
Z is composition ring AACRing atom, preferably oxygen atom.
nZThe integer of expression more than 1, preferably 1~6, more preferably 1 or 2, more preferably 1.
nZFor more than 2 integer when, multiple Z may be the same or different, and at least one preferably wherein is oxygen atom.
A be using in A " ＞ C=" are as ring AACRing atom group, 2 singly-bounds of the carbon atom respectively with ring
AACRing atom bonding and above-mentioned carbon atom introduces ring AACIn.
A specifically represents ＞ C=CRY1RY2, ＞ C=S, ＞ C=O or ＞ C=NRY3.Wherein, RY1And RY2Independently
Ground represents substituent.Also, RY3Represent hydrogen atom or substituent.RY1~RY3Desirable substituent is not particularly limited, for example,
Above-mentioned formula (I) R can be enumerated1aThe substituent that can have.
RY1And RY2It can be mutually bonded and form ring.RY1And RY2The ring formed is not particularly limited, and can be and above-mentioned ring
AACIdentical ring.
nAMore than 0 integer is represented, according to ring AACForm (for example, the presence or absence of aromatic series), exist take more than 1 it is whole
Several situations.nAIt is preferred that represent 0~3 integer, more preferably 0 or 1, more preferably 0.
Ring AACCarbon atom and Z, and above-mentioned n are included as ring atomAFor more than 1 integer when, also comprising in A
Carbon atom (＞ C=).
Ring AACFirst number be not particularly limited, but preferably ring AACFor 3~8 yuan of rings, preferably 5 yuan of rings or 6 yuan of rings.
As this ring AAC, for example, heteroaromatic and aliphatic heterocycle, preferably heteroaromatic can be enumerated.
Heteroaromatic is the heterocycle for indicating aromatic series.Aliphatic heterocycle refers to the heterocycle beyond heteroaromatic,
Representative examples of saturated aliphatic heterocycle can be enumerated and the unsaturated aliphatic heterocycle of aromatic series is not shown.
As heteroaromatic, for example, thiphene ring or furan nucleus can be enumerated.
As representative examples of saturated aliphatic heterocycle, for example, oxetanes ring, tetrahydrofuran ring, amylene oxide ring, dioxy can be enumerated
Penta ring, dioxanes ring, vulcanization cyclopropane ring, thiophane ring, vulcanization pentamethylene ring (tetrahydric thiapyran ring), dithiolane etc..
As unsaturated aliphatic heterocycle, for example, dihydrofuran ring, dihydropyran ring, dihydro-thiophene ring, dihydro can be enumerated
Thiapyran ring, thiapyran ring, two mercaptan (dithiole) etc..
In the present invention, R described laterACWhen being bonded each other and forming ring, RACThe ring formed each other and ring AACAs thick
Ring.As this condensed ring, according to RACSpecies, RACThe number of rings formed each other, take various structures.For example, benzothiophene ring,
Dibenzothiophenes ring, benzene thiophene ring, thienothiophene ring, benzofuran ring, dibenzofurans ring, Dihydrobenzofuranes ring
Deng.
Ring AACThe heteroaromatic of the preferably heteroaromatic of 5 yuan of rings or 6 yuan of rings, more preferably 5 yuan of rings, further
Preferably thiphene ring or furan nucleus, especially preferably furan nucleus.
RACRepresent substituent.RACDesirable substituent is not particularly limited, for example, above-mentioned formula (I) R can be enumerated1aCan
The substituent having.
RACDesirable substituent is for example, alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, alkoxy, alkylthio group also include quilt
R1aThe group for the substituent substitution that can have.As this group, alkyl, alkenyl, alkynes are substituted by halogen atom for example, can enumerate
Base, aryl, heterocyclic radical, alkoxy or alkylthio group each base hydrogen atom group (the referred to as group with halogen atom), pass through
Group of the hydrogen atom of alkyl substituting aromatic base or heterocyclic radical etc..
On RACDesirable substituent, wherein, preferably alkyl, alkenyl, alkynyl, aryl, heterocyclic radical, alkoxy, alkane sulphur
Base, halogen atom or the group with halogen atom, more preferably alkyl, halogen atom or the group with halogen atom, further preferably
For the alkyl of carbon number more than 5, halogen atom or the group with halogen atom.
Alkyl is preferably the alkyl that carbon number is 1~30, and more preferably carbon number is 5~18 alkyl, further
Preferably carbon number is 5~12 alkyl.The alkyl can be that straight chain can also be side chain.As alkyl, for example, can enumerate
Methyl, ethyl, the straight chain either amyl group of the butyl of the propyl group of side chain, straight chain or side chain, straight chain or side chain, straight chain or branch
The hexyl of chain, the straight chain either octadecyl of the dodecyl of the decyl of side chain, straight chain or side chain or straight chain or side chain.
Alkenyl, alkynyl, aryl, heterocyclic radical (heteroaryl), alkoxy and alkylthio group implication respectively with R1aAlkenyl, alkynes
Base, aryl, heteroaryl, alkoxy and alkylthio group are identical.When heterocyclic radical is aliphatic heterocycle, its implication and above-mentioned ring AACFat
Race's heterocycle is identical.
Halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms or iodine atom, preferably fluorine atom, chlorine atom, bromine atoms.
In group with halogen atom, as long as substituting the quantity at least 1 of the halogen atom of hydrogen atom, then special limit is had no
It is fixed.The group that preferably all hydrogen atoms are substituted by halogen atom.The halogen atom of substitution hydrogen atom is also not particularly limited, and can be enumerated
Fluorine atom, chlorine atom, bromine atoms or iodine atom, preferably fluorine atom.
Group with halogen atom substitutes the group (halogenated alkyl) of the hydrogen atom of alkyl preferably by halogen atom, enters one
The group (fluorinated alkyl) that step substitutes preferably by fluorine atom.As fluorinated alkyl, for example, it is preferable to be trifluoromethyl, trifluoro
Ethyl, heptafluoropropyl, seven fluorine isopropyls, 15 fluorine heptyl, ten trifluoro heptyl etc..The carbon number of halogenated alkyl has no special limit
It is fixed, preferably 1~30, more preferably 1~10, more preferably 1.Halogenated alkyl is preferably that all hydrogen atoms are taken by fluorine atom
The perfluoroalkyl in generation.
nRFor more than 2 integer when, multiple RACIt may be the same or different.Also, 2 adjacent RACIt can be mutually bonded and shape
Cyclization.
RACIn ring AACThe position of substitution be not particularly limited, ring atom preferably adjacent with Z.
nRRepresent more than 0 integer, preferably 0~7 integer, more preferably 0~4 integer, more preferably 1 or
2.Wherein, Z is sulphur atom, and nZFor 1 when, nRRepresent more than 1 integer, preferably 1~7 integer, more preferably 1~4 it is whole
Number, more preferably 1 or 2.
Compound AC can synthesize according to usual way, additionally it is possible to use commercially available product.
Compound AC described below concrete example, but the present invention is not limited to these.
[chemical formula 7]
The ＞ of ＜ hole transmission layers 3
In the photo-electric conversion element of the present invention, in the 1st electrode 1 and the 2nd electrode 2 as photo-electric conversion element 10A~10D
Between have hole transmission layer 3 mode be one of preferred embodiment.If compound layer 5 contacts (stacking) with hole transmission layer 3,
Compound AC above-mentioned effect can be effectively obtained.
Hole transmission layer 3 has the layer of function, preferably solid-like that electronics is supplemented to the oxysome of light absorber.Hole
Transmitting layer 3 is preferably disposed between the electrode 2 of photosensitive layer 13 and the 2nd of the 1st electrode 1.
Formed hole transmission layer 3 hole mobile material be not particularly limited, can enumerate the inorganic material such as CuI, CuNCS and
Organic hole transport material described in the paragraph 0209~0212 of Japanese Unexamined Patent Publication 2001-291534 publications etc..As having
Machine hole mobile material, preferably enumerate the electroconductive polymers such as polythiophene, polyaniline, polypyrrole and polysilane, 2 rings share
C, Si etc. takes the aromatic amines compounds such as the spiro-compound of the central atom of tetrahedral structure, triarylamine, Sanya phenylating
Compound, nitrogen-containing heterocycle compound or liquid crystal liquid crystal property cyanogen compound.
Hole mobile material is preferably capable carrying out solution coating and turns into the organic hole transport material of solid-like, specifically
For, can enumerate 2,2 ', 7,7 '-four-(bis--P-nethoxyaniline of N, N-) -9,9- spiro-bisfluorenes (also referred to Spiro-OMeTAD),
Poly- (3- hexyl thiophene -2,5- diyls), 4- (diethylamino) benzaldehydes diphenyl hydrazone, Polyethylene di (PEDOT)
Deng.
The thickness of hole transmission layer 3 is not particularly limited, preferably less than 50 μm, more preferably 1nm~10 μm, further
Preferably 5nm~5 μm, especially preferably 10nm~1 μm.
The ＞ of ＜ electron transfer layers 4
In the photo-electric conversion element of the present invention, as photo-electric conversion element 10E between the 1st electrode 1 and the 2nd electrode 2
Mode with electron transfer layer 4 is also one of preferred embodiment.In which, if compound layer 5 contacts with electron transfer layer 4
(stacking), then it can also effectively obtain compound AC above-mentioned effect.
In electron transfer layer 4, the connection object of electronics is the 2nd electrode, and the position formed is different, in addition, with
Above-mentioned electron transfer layer 15 is identical.
The ＞ of the 2nd electrodes of ＜ 2
2nd electrode 2 plays a role as negative or positive electrode in solar cells.2nd electrode 2 as long as there is electric conductivity,
Then it is not particularly limited, usually can be set to and the identical structure of conductive support 11.When can substantially ensure that intensity, supporting mass
11a is simultaneously nonessential.
As the structure of the 2nd electrode 2, the preferably higher structure of current collection effect.In order that light reaches photosensitive layer 13, it is conductive
Property supporting mass 11 and at least one in the 2nd electrode 2 must be essentially transparent.In the solar cell of the present invention, preferably lead
Electrical supporting mass 11 is transparent and makes sunshine incident from supporting mass 11a sides.Now, further preferred 2nd electrode 2 has reflection
The property of light.
As forming the material of the 2nd electrode 2, for example, can enumerate platinum (Pt), golden (Au), nickel (Ni), copper (Cu), silver-colored (Ag),
The metal oxidation of the metals such as indium (In), ruthenium (Ru), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), aluminium (Al), above-mentioned electric conductivity
Thing, carbon material and conductibility macromolecule etc..As carbon material, as long as carbon atom bonds together and formed and conductive material
Material, for example, fullerene, CNT, graphite, graphene etc. can be enumerated.
As the 2nd electrode 2, preferably metal or conductive metal oxide thin film (film formed comprising evaporation) or
Glass substrate or plastic base with the film.As glass substrate or plastic base, it is however preferred to have gold or platinum
The glass or evaporation of film have the glass of platinum.
The thickness of 2nd electrode 2 is not particularly limited, preferably 0.01~100 μm, more preferably 0.01~10 μm,
Especially preferably 0.01~1 μm.
＜ other structures ＞
In the present invention, in order to prevent the 1st contact with the 2nd electrode 2 of electrode 1, additionally it is possible to instead of the grade of barrier layer 14 or with resistance
Barrier 14 etc. is used together sept or separator.
Also, hole blocking layer can be set between the 2nd electrode 2 and hole transmission layer 3.
《Solar cell》
The solar cell of the present invention is formed using the photo-electric conversion element of the present invention.Such as shown in Fig. 1~Fig. 6,
The photo-electric conversion element 10 that can will be set external circuit 6 and form is used as solar cell.(electric conductivity supports with the 1st electrode 1
Body 11) and the 2nd electrode 2 connection external circuit can not especially limitedly use known to external circuit.
The solar cell of the present invention in order to prevent the deterioration of construct and evaporation etc. and it is preferred that with polymer or binding agent
Etc. seal side.
Have as described above, the photo-electric conversion element and solar cell of the present invention possess on surface with above-mentioned formula (AC) table
1st electrode of the compound shown, shows excellent durability.
《The manufacture method of photo-electric conversion element and solar cell》
The photo-electric conversion element and solar cell of the present invention can be according to known manufacture method, such as non-patent literature
Method manufacture described in 1 grade.
Hereinafter, the photo-electric conversion element of the present invention and the manufacture method of solar cell are briefly described.
The photo-electric conversion element of the present invention and the manufacture method (hereinafter referred to as manufacture method of the invention) of solar cell
In, as long as there is making with electric comprising the 1st using the perovskite compound that above-mentioned formula (1) represents as the photosensitive layer of light absorber
The process that pole contacts with containing the liquid of compound represented with above-mentioned formula (AC), then Other Engineering etc. be not particularly limited.
In the manufacture method of the present invention, first on the surface of conductive support 11, formed as needed barrier layer 14,
It is at least one in porous layer 12, electron transfer layer 15 and hole transmission layer 16.
Barrier layer 14 is such as can be by the way that the dispersion containing above-mentioned insulating properties material or its precursor compound is coated with
In the surface of conductive support 11, and the formation such as the method by burning till or spray pyrolysis.
The material for forming porous layer 12 uses preferably as particulate, is more preferably used as and contains fine-grained dispersion
To use.
As the method for forming porous layer 12, it is not particularly limited, for example, damp process, dry process, other method can be enumerated
(for example, Chemical Review, volume 110, the method described in page 6595 (2010 annual)).In these methods, preferably exist
After the surface of conductive support 11 or the surface coating dispersion (slurry) on barrier layer 14, such as preferably in atmosphere,
Burnt till at a temperature of 100~800 DEG C 10 minutes~10 hours.Thereby, it is possible to be adhering to each other particulate.
When repeatedly being burnt till, preferably the temperature (firing temperature beyond last) burnt till beyond last burn till is set
Carried out for temperature less than last firing temperature (last firing temperature)., can will for example, during using titania slurry
Firing temperature beyond last is set as in the range of 50~300 DEG C.Further, it is possible to last firing temperature is set as
In the range of 100~600 DEG C, higher than the firing temperature beyond last.When using glass support as supporting mass 11a, burn till
Temperature is preferably 60~500 DEG C.
The coating weight of porous material during formation porous layer 12 is appropriate according to the thickness of porous layer 12 and application frequency etc.
Setting, is not particularly limited.Every 1m of conductive support 112Surface area on porous material coating weight it is for example preferred
For 0.5~500g, more preferably 5~100g.
Electron transfer layer 15 is set or during hole transmission layer 16, can respectively with hole transmission layer 3 described later or electronics
The identical method of transport layer 4 is formed.
Then, photosensitive layer 13 is set.
Damp process and dry process can be enumerated by setting the method for photosensitive layer 13, be not particularly limited.It is preferably wet in the present invention
Formula method, for example, it is preferable to make the method that it is contacted with the light absorber solution containing absorbent.In this method, use is prepared first
In the light absorber solution for forming photosensitive layer 13.Light absorber solution contains the MX of the raw material as above-mentioned perovskite compound2
With AX.Wherein, A, M and X implication are identical with A, M and X of above-mentioned formula (I).In the light absorber solution, MX2With AX mole
Than according to the appropriate adjustment of purpose.When forming perovskite compound as light absorber, AX and MX2Mol ratio be preferably 1:1~
10:1.The light absorber solution can be with defined mixed in molar ratio AX and MX2Afterwards, preferably prepared by heating.Should
Formation liquid is usually solution but it is also possible to be suspension.The condition of heating is not particularly limited, and heating-up temperature is preferably 30~
200 DEG C, more preferably 60~150 DEG C.Heat time is preferably 0.5~100 hour, more preferably 1~3 hour.
Solvent or decentralized medium can use solvent described later or decentralized medium.
Then, make prepared light absorber solution with surface formed photosensitive layer 13 layer (in photo-electric conversion element 10,
Any layer in porous layer 12, barrier layer 14, electron transfer layer 15 or hole transmission layer 16) surface contact.Specifically, it is excellent
Choosing is coated or impregnated with light absorber solution.Thus, perovskite compound forms (accumulation or absorption etc.) in porous layer 12, barrier layer
14th, the surface of electron transfer layer 15 or hole transmission layer 16.Contact Temperature is preferably 5~100 DEG C, and dip time is preferably 5 seconds
~24 hours, more preferably 20 seconds~1 hour.When making be coated with light absorber solution drying, above-mentioned drying is preferably based on
The drying of heat, generally by being heated to 20~300 DEG C, being preferably heated to 50~170 DEG C to make its drying.
Also, photosensitive layer can also be formed according to the synthetic method of above-mentioned perovskite compound.
It is respectively coated moreover, can also enumerate and (includes infusion process) the AX solution containing above-mentioned AX and contain above-mentioned MX2MX2
Solution, and the method being dried as needed.In this method, any solution is first coated with, but be preferably first coated with MX2It is molten
Liquid.AX and MX in this method2Mol ratio, application conditions and drying condition it is same as mentioned above.In this method, additionally it is possible to
Instead of above-mentioned AX solution and above-mentioned MX2The coating of solution and AX or MX is deposited2。
Moreover, as other methods, compound or the mixing of the solvent using above-mentioned light absorber solution is removed can be enumerated
The dry processes such as the vacuum evaporation of thing.Above-mentioned AX and above-mentioned MX is simultaneously or sequentially deposited for example, can also enumerate2Method.
Thus, light absorber is formed, turns into photosensitive layer 13.
In the manufacture method of the present invention, then, compound AC is arranged to the surface of the 1st electrode.
When compound AC is arranged at into the surface of the 1st electrode, the liquid containing compound AC is used.The liquid can be liquid
The compound AC of shape itself, and can be that solution can also be suspension (dispersion liquid).Solvent or decentralized medium have no spy
Do not limit, for example, solvent or decentralized medium described later, preferably isopropanol can be enumerated.The concentration of compound AC in a liquid is simultaneously
It is not particularly limited, for example, it is preferable to be 0.01~100 mass %, more preferably 0.1~1 mass %.
The method for making prepared liquid be contacted with the surface of the 1st electrode is not particularly limited, for example, can enumerate the 1st
The method of the surface coating liquid body of electrode or the method being impregnated in the 1st electrode in liquid.Coating method can be enumerated described later each
Kind method.
The temperature being coated or impregnated with is preferably 5~100 DEG C.As long as think within the range, to be then able to maintain that calcium titanium ore bed
Structure.
Dip time is preferably 0.1 second~24 hours, more preferably 5 seconds~1 hour.
After being coated or impregnated with, preferred pair liquid is dried.Drying condition is not particularly limited.Drying temperature is for example excellent
Elect 20~200 DEG C, more preferably 25~120 DEG C as.Drying time is for example preferably 1 minute~10 hours, more preferably 5 minutes
~1 hour.
As the coating weight of the compound AC in the process, suitably determined according to compound AC species etc., have no spy
Do not limit.In the present invention, with least a portion on the surface of the 1st electrode by the compound AC (compound layer 5) of above-mentioned amount
The mode of covering determines.
It is preferred that hole transmission layer 3 or electron transfer layer 4 are formed on the 1st electrode for be thusly-formed compound layer.
Hole transmission layer 3 can by be coated with the hole mobile material solution containing hole mobile material and be dried come
Formed.Excellent and when there is porous layer 12 easily from the viewpoint of intrusion to the hole inside of porous layer 12, the hole transport from coating
The concentration of the preferred hole mobile material of material solution is 0.1~1.0M (mole/L) solution.
Electron transfer layer 4 can by be coated with the electron transport material solution containing electron transport material and be dried come
Formed.
The 2nd electrode 2 is formed after hole transmission layer 3 or electron transfer layer 4 is formed to manufacture photo-electric conversion element.
The thickness of each layer can suitably change the concentration of each dispersion liquid or solution, application frequency adjusts.For example, film is set
During thicker photosensitive layer 13B and 13C, repeatedly it is coated with light absorber solution and is simultaneously dried.
Above-mentioned each dispersion liquid and solution can be respectively as needed containing additives such as dispersing aid, surfactants.
As the solvent or decentralized medium used in the manufacture method of photo-electric conversion element and solar cell, can enumerate day
Solvent described in this JP 2001-291534 publications, but it is not particularly limited to this.It is preferably organic molten in the present invention
Agent, more preferably alcoholic solvent, amide solvent, nitrile solvent, hydrocarbon solvent, interior ester solvent, halogen solvent, thioether solvent and these
Mixed solvent of more than two kinds.As mixed solvent, preferably alcoholic solvent is with being selected from amide solvent, nitrile solvent or hydrocarbon solvent
The mixed solvent of solvent.Specifically, preferably methanol, ethanol, isopropanol, gamma-butyrolacton, n- propyl group thioether, chlorobenzene, second
Nitrile, dimethylformamide (DMF) or dimethyl acetamide or these mixed solvent.
The coating method of the solution or dispersant that form each layer is not particularly limited, and spin-coating method, mould can be utilized to extrude
Method, knife coating, stick coating method, screen painting, mould printing, rolling method, curtain coating, spraying process, dip coating, ink jet printing method, leaching
Coating method known to stain method etc..Wherein, preferably spin-coating method, screen painting method, infusion process etc..
The efficiency such as the photo-electric conversion element of the present invention can be annealed as needed, light infiltration, placement under oxygen atmosphere are steady
Determining processing.
The photo-electric conversion element made as described above external circuit 6 can be connected to the 1st electrode 1 (transparency electrode 11b) and
2nd electrode 2 is used as solar cell.
Embodiment
Hereinafter, the present invention is described in more detail according to embodiment, but the present invention is not limited to following embodiments.
Synthesis example
Each compound AC, thiophene and the pyridine used in following embodiments is prepared.
On the compound AC that can not be obtained, synthesized according to the method described in following documents.
For example, the document described below referred in the synthesis of following compounds.
Compound AC-3 and AC-11：tetrahedron,2013,vol69,No.38,p.8191-8198
Compound AC-5：Organic Letters,2011,vol.13,No.20,p.5464-5467
Compound AC-14：Journal of Agricultural and Food Chemistry,2009,vol.57,
No.20,p.9607-9612
Compound AC-15：Organic and Biomolecular Chemistry,2014,vol.12,No.34,
p.6661-6671
Compound AC-17：Organic Letters, 2001, vol.3, No.19,2997-2999 and Journal of
Fluorine Chemistry,1990,vol.46,No.3,p.423-431
Compound AC-19:Tetrahedron Letters,2011,vol.52,No.38,p.4965-4966
Compound AC-22:European Journal of Organic Chemistry,2008,No.21,p.3668-
3672
Compound AC-23:Heterocycles, 1997, vol.46, No.1,209-214 and Chemical
Communications,2005,No.26,p.3295-3297
Embodiment 1
(manufacture of photo-electric conversion element (specimen coding 101))
According to step described below, the photo-electric conversion element 10A shown in Fig. 1 has been manufactured.In addition, the thickness of photosensitive layer 13
When larger, corresponding to the photo-electric conversion element 10B shown in Fig. 2.
The making ＞ of ＜ conductive supports 11
The SnO doped with fluorine is formed on glass substrate (supporting mass 11a, thickness 2mm)2Conducting film (transparency electrode 11b,
Thickness 300nm) make conductive support 11.
The preparation ＞ of ＜ barrier layers solution
With the 15 mass % aqueous isopropanol (Aldriches of double (acetylacetone,2,4-pentanedione) titaniums of n-butyl alcohol dilution diisopropoxy
Manufacture) it is prepared for 0.02M barrier layer solution.
The formation ＞ on ＜ barrier layers 14
Using prepared 0.02M barrier layer solution, by spray pyrolysis, at 450 DEG C, supported in electric conductivity
The SnO of body 112The barrier layer 14 (thickness 50nm) comprising titanium oxide is formd on conducting film.
The preparation ＞ of ＜ titania slurries
Alcohol dispersion liquid addition ethyl cellulose, dodecylic acid and terpene to titanium oxide (anatase, average grain diameter 20nm)
Product alcohol is prepared for titania slurry.
The formation ＞ of ＜ porous layers 12
Prepared titania slurry is coated on barrier layer 14 by screen painting method, in atmosphere, at 500 DEG C
Burn till 3 hours.Afterwards, the sintered body of the titanium oxide obtained is impregnated in 40mM TiCl4After the aqueous solution, add at 60 DEG C
Heat 1 hour, then heats 30 minutes at 500 DEG C, TiO is included so as to form2Porous layer 12 (thickness 250nm).
＜ photosensitive layers 13A formation ＞
In flask, by 40% methanol solution (27.86mL) of methyl amine and the water of 57 mass % hydrogen iodide at 0 DEG C
After solution (iodate hydracid, 30mL) stirs 2 hours, concentrated to obtain CH3NH3I crude product.By what is obtained
CH3NH3I crude product is dissolved in ethanol, and is recrystallized with Anaesthetie Ether, filters out obtained crystal, is carried out at 60 DEG C
5 hours be dried under reduced pressure purifies CH to obtain3NH3I。
Then, CH will be purified3NH3I and PbI2It is set to molar ratio computing 3：1, in DMF, it is small at 60 DEG C to be stirred 12
Afterwards, filtered with polytetrafluoroethylene (PTFE) (PTFE) injection filter to be prepared for 40 mass % light absorber solution A.
Prepared light absorber solution A is coated in conduction by film forming by spin-coating method (being coated with 60 seconds with 2000rpm)
Property supporting mass 11 on porous layer 12 on after, 60 points are carried out to the light absorber solution A that is coated with 100 DEG C by heating plate
The drying of clock, so as to which there is provided include CH3NH3PbI3The photosensitive layer 13A of perovskite compound (thickness 300nm is (comprising porous
The thickness 250nm of layer 12)).
So the 1st electrode 1A is made.
＜ compound layers 5A formation ＞
Then, by spin-coating method (with 3000rpm be coated with 30 seconds) 25mm angles the 1st electrode 1A surface painting compound
After the AC-1 μ L of 0.1 mass % aqueous isopropanols 80, to the solution being coated with, carried out 30 minutes with 100 DEG C by heating plate
Drying.It has been thusly-formed compound layer 5A.
Wherein, confirm that the be coated with the aqueous isopropanol containing compound AC-1 the 1st is electric using HPLC as described above
Pole 1A surface, as a result, 1.8mg/m be present on photosensitive layer 13A surface2Compound AC-1.
The preparation ＞ of ＜ hole mobile material solution
Chlorobenzene (1mL) is dissolved in using as the spiro-OMeTAD of hole mobile material (180mg).To the chlorobenzene solution,
Double (trifyl) imine lithiums (170mg) are dissolved in the μ L of acetonitrile solution 37.5 and tert-butyl group pyrrole of acetonitrile (1mL) by addition
Pyridine (TBP, 17.5 μ L) is simultaneously mixed, so as to be prepared for hole transmission layer solution.
＜ hole transmission layers 3A formation ＞
Then, on the compound layer 5A being formed on the 1st electrode 1A surface, prepared sky is coated with by spin-coating method
Cave transport layer solution and drying, so as to the hole transmission layer 3A (thickness 100nm) of film forming solid-like.
The making ＞ of the electrodes 2 of ＜ the 2nd
By vapour deposition method on hole transmission layer 3A gold evaporation, so as to make the 2nd electrode 2 (thickness 100nm).
So photo-electric conversion element 10A (specimen coding 101) is manufactured.
On each thickness, according to the above method, it is determined by SEM observations.
(manufacture of photo-electric conversion element (specimen coding 102~119, c01 and c02))
In the manufacture of photo-electric conversion element (specimen coding 101), used instead of compound AC-1 and contained table 1 below respectively
" compound represented with formula (AC) " column described in compound aqueous isopropanol or uncoated containing compound AC-1's
Aqueous isopropanol (specimen coding c02), in addition, with the manufacture identical side with photo-electric conversion element (specimen coding 101)
Method, the photo-electric conversion element (specimen coding 102~119) of the present invention and the photo-electric conversion element for comparing have been manufactured respectively
(specimen coding c01 and c02).
On specimen coding 102~119, after compound layer 5A is formed, it is thus identified that exist on the 1st electrode 1A surface
Each compound AC.
(manufacture of photo-electric conversion element (specimen coding 120))
In the manufacture of photo-electric conversion element (specimen coding 101), compound AC-2 is used instead of compound AC-1, and replace
Light absorber solution A using following light absorber solution Bs and forms photosensitive layer 13A according to following methods, in addition, with
The manufacture identical method of photo-electric conversion element (specimen coding 101) has manufactured the photo-electric conversion element (specimen coding of the present invention
120)。
Formed after compound layer 5A, it is thus identified that compound AC-2 be present on the 1st electrode 1A surface.
The preparation ＞ of ＜ light absorber solution Bs
In flask, by 40% ethanol solution (36g) of ethylamine and the aqueous solution of 57 mass % hydrogen iodide at 0 DEG C
After (iodate hydracid, 72g) is stirred 2 hours, concentrated to obtain CH3CH2NH3I crude product.By what is obtained
CH3CH2NH3I crude product is dissolved in ethanol, and is recrystallized with Anaesthetie Ether.Separated out crystal is filtered out, at 60 DEG C
It is lower carry out 12 hours be dried under reduced pressure obtain purification CH3CH2NH3I.Then, CH will be purified3CH2NH3I and PbI2Be set to
Molar ratio computing 2:1, in DMF, it is stirred at 60 DEG C after 5 hours, is filtered with PTFE injection filters, thus made
For 40 mass % light absorber solution B.
On porous layer 12, by spin-coating method (be coated with 60 seconds with 2000rpm) the prepared light absorber solution B of coating it
Afterwards, carry out the drying of 40 minutes to the light absorber solution B that is coated with 140 DEG C by heating plate, be thus provided with comprising
(CH3CH2NH3)2PbI4Perovskite compound photosensitive layer 13A (thickness 300nm (the thickness 250nm for including porous layer 12)).
(manufacture of photo-electric conversion element (specimen coding 121))
It is molten using following light absorbers instead of light absorber solution A in the manufacture of photo-electric conversion element (specimen coding 112)
Liquid C, in addition, the photoelectricity of the present invention is manufactured in the manufacture identical method with photo-electric conversion element (specimen coding 112)
Conversion element (specimen coding 121).
The photosensitive layer obtained contains with CH3NH3PBI(3-n)Cln(n represents 0.001~2 number.) represent perovskite
Compound.
Formed after compound layer 5A, it is thus identified that compound AC-15 be present on the 1st electrode 1A surface.
The preparation ＞ of ＜ light absorber solution Cs
In flask, by 40% methanol solution (27.86mL) of methyl amine and the water of 57 mass % hydrogen iodide at 0 DEG C
Solution (iodate hydracid, 30mL) is concentrated to obtain CH after stirring 2 hours3NH3I crude product.By what is obtained
CH3NH3I crude product is dissolved in ethanol, and is recrystallized with Anaesthetie Ether, filters out obtained crystal, is carried out at 60 DEG C
5 hours be dried under reduced pressure, CH is purified so as to obtain3NH3I.Then, CH will be purified3NH3I and PbCl2With molar ratio computing 3:1,
In DMF, it is stirred after 12 hours, is filtered with PTFE injection filters, so as to be prepared for 40 mass % light at 60 DEG C
Absorbent solution C.
(manufacture of photo-electric conversion element (specimen coding c03))
In the manufacture of photo-electric conversion element (specimen coding 121), the uncoated aqueous isopropanol containing compound AC-15,
In addition, the photoelectricity manufactured in the manufacture identical method with photo-electric conversion element (specimen coding 121) for compared with turns
Change element (specimen coding c03).
(manufacture of photo-electric conversion element (specimen coding c04))
In the manufacture of photo-electric conversion element (specimen coding 121), the isopropyl containing pyridine has been used instead of compound AC-15
Alcoholic solution, in addition, manufactured in the manufacture identical method with photo-electric conversion element (specimen coding 121) for compared with
Photo-electric conversion element (specimen coding c04).
The evaluation ＞ of ＜ durability
So that the photo-electric conversion element of each specimen coding is manufactured into 10 measured bodies with above-mentioned manufacture method identical method.Point
It is other that battery behavior experiment is carried out to 10 measured bodies, determine electric current.Also, using the average value of 10 measured bodies as each examination
The initial current of the photo-electric conversion element of sample numbering.Test, utilize solar simulator " WXS-85H " on battery behavior
(WACOM CO., LTD. manufacture), from the xenon light irradiation 1000W/m by AM1.5 wave filters2Simulated solar irradiation carry out.
I-E characteristic is determined using I-V testers.
Then, respectively by 10 measured bodies of each specimen coding humidity 50RH%, 30 DEG C of temperature constant temperature and humidity cabinet in
After standing 30 hours, battery behavior experiment is carried out in the same manner as described above, thus determines electric current.By being averaged for 10 measured bodies
Value is as the electric current after the standing of the photo-electric conversion element of each specimen coding.
The durability of photo-electric conversion element is according to the rate of descent of the electric current calculated by following formula, according to following evaluation bases
Standard is evaluated.It is the qualified rank of this experiment in the metewand of durability, more than " C ".Show the result in table 1 below.
Rate of descent (%)=[(electric current after initial current-standing)/(initial current)] × 100
- durability evaluation benchmark-
A：Rate of descent is less than 20%
B+：Rate of descent is 20% less than 24%
B：Rate of descent is 24% less than 28%
C+：Rate of descent is 28% less than 32%
C：Rate of descent is 32% less than 36%
D+：Rate of descent is 36% less than 40%
D：Rate of descent is more than 40%
[table 1]
Following content as can be known from the results of Table 1.
That is, even perovskite compound to be used as to the photo-electric conversion element of light absorber, have on the surface of the 1st electrode
The rate of descent of the electric current of compound AC (compound layer) photo-electric conversion element of the invention is smaller, shows excellent durable
Property.
It is being used as light absorber using containing chlorine atom and iodine atom this 2 kinds of perovskite compounds as anionic property atom
Photo-electric conversion element in, also obtain this excellent durability.
Especially, if the n of formula (AC)AFor 0 and RACFor halogen atom, carbon number more than 5 alkyl or with halogen atom base
Group's (halogenated alkyl), then the improvement of durability is larger.If the also, n of formula (AC)AIt is oxygen atom for 0 and Z, then especially exists
The ring A of formula (AC)ACFor furan nucleus when, the improvement of durability further becomes big.
In contrast, perovskite compound is used as in the photo-electric conversion element of light absorber, with thiophene or pyridine to the 1st
The photo-electric conversion element (specimen coding c01 and c04) that the surface of electrode is handled is specific with not having on the surface of the 1st electrode
The rate of descent of the electric current of compound AC photo-electric conversion element (specimen coding c02 and c03) is larger, and durability is simultaneously insufficient.
Embodiment 2
(manufacture of photo-electric conversion element (specimen coding 201))
According to step described below, the photo-electric conversion element shown in Fig. 1 has been manufactured in the same manner as in Example 1
10A。
In the manufacture of photo-electric conversion element (specimen coding 112), following light absorbers have been used instead of light absorber solution A
Solution D simultaneously forms photosensitive layer 13A according to following methods, in addition, with the system with photo-electric conversion element (specimen coding 112)
Make the photo-electric conversion element (specimen coding 201) that identical method has manufactured the present invention.
Formed after compound layer 5A, it is thus identified that compound AC-15 be present on the 1st electrode 1A surface.
The preparation ＞ of ＜ light absorber solution Ds
In flask, by 40% methanol solution (27.86mL) of methyl amine and the water of 57 mass % hydrogen iodide at 0 DEG C
After solution (iodate hydracid, 30mL) stirs 2 hours, concentrated to obtain CH3NH3I crude product.By what is obtained
CH3NH3I crude product is dissolved in ethanol, and is recrystallized with Anaesthetie Ether, filters out obtained crystal, is carried out at 60 DEG C
5 hours be dried under reduced pressure, CH is purified so as to obtain3NH3I.Then, CH will be purified3NH3I and PbI2With SnI2With mol ratio 2:
0.9:0.1, in gamma-butyrolacton, it is stirred after 12 hours, is filtered with PTFE injection filters to be prepared at 60 DEG C
40 mass % light absorber solution D.
On porous layer 12, (60 seconds are coated with 2000rpm, are then coated with 60 seconds with 3000rpm) coating by spin-coating method
After prepared light absorber solution D, the light absorber solution D being coated with is carried out 80 minutes with 100 DEG C by heating plate
Drying, include CH so as to form3NH3Pb0.9Sn0.1I3Perovskite compound photosensitive layer 13A.
(manufacture of photo-electric conversion element (specimen coding c21))
In the manufacture of photo-electric conversion element (specimen coding 201), the aqueous isopropanol containing compound AC-15 is not coated with
In the 1st electrode 1A surface, in addition, to be manufactured with the manufacture identical method of photo-electric conversion element (specimen coding 201)
It is used for the photo-electric conversion element (specimen coding c21) compared.
The evaluation ＞ of ＜ durability
Respectively to the photo-electric conversion element (10 measured bodies) of each specimen coding so manufactured, in humidity 10RH%, temperature
10 hours are stood in the constant temperature and humidity container of 20 DEG C of degree, in addition, in the same manner as the evaluation ＞ of the ＜ durability of embodiment 1
It has rated durability.It is the qualified rank of this experiment in the metewand of durability, more than " C ".Show the result in table 2.
[table 2]
It is clear that from the result of table 2, using containing tin, this 2 kinds of perovskite compounds as metallic atom are used as light with lead
In the photo-electric conversion element of absorbent, sufficient durability also obtain.
On the other hand, do not have the durability of specific compound AC photo-electric conversion element on the surface of the 1st electrode not
Fully.
Embodiment 3
(manufacture of photo-electric conversion element (specimen coding 301))
According to step described below, the photo-electric conversion element 10C shown in Fig. 3 has been manufactured.
In the manufacture of photo-electric conversion element (specimen coding 112), it is not provided with porous layer 12 but is set on barrier layer 14
Photosensitive layer 13C, photosensitive layer 13C and hole transmission layer 3B thickness are changed to following thickness respectively, in addition, with photoelectricity
The manufacture identical method of conversion element (specimen coding 112) has manufactured the photo-electric conversion element 10C (specimen codings of the present invention
301)。
In photo-electric conversion element 10C (specimen coding 301), photosensitive layer 13C thickness is 250nm, hole transmission layer 3B
Thickness be 100nm.
Formed after compound layer 5B, it is thus identified that compound AC-15 be present on the 1st electrode 1C surface.
(manufacture of photo-electric conversion element (specimen coding c31))
In the manufacture of photo-electric conversion element (specimen coding 301), the aqueous isopropanol containing compound AC-15 is not coated with
In the 1st electrode 1C surface, in addition, to be manufactured with the manufacture identical method of photo-electric conversion element (specimen coding 301)
It is used for the photo-electric conversion element (specimen coding c31) compared.
The evaluation ＞ of ＜ durability
It is resistance to the ＜ of embodiment 1 respectively to the photo-electric conversion element (10 measured bodies) of each specimen coding so manufactured
The evaluation ＞ of long property similarly have rated durability.Show the result in table 3.
[table 3]
It is clear that, perovskite compound is used as in the photo-electric conversion element of light absorber, even if not from the result of table 3
Porous layer is set, also shows that excellent durability.
On the other hand, do not have the durability of specific compound AC photo-electric conversion element on the surface of the 1st electrode not
Fully.
Embodiment 4
(manufacture of photo-electric conversion element (specimen coding 401))
According to step described below, the photo-electric conversion element 10E shown in Fig. 5 has been manufactured.
The making ＞ of ＜ conductive supports 11
Tin-doped indium oxide film (ITO, transparency electrode 11b, thickness are formed on glass substrate (supporting mass 11a, thickness 2mm)
300nm), so as to having made conductive support 11.
The formation ＞ of ＜ hole transmission layers 16
Poly- (3,4- ethylene dioxythiophene)-poly- (styrene sulfonic acid) (PEDOT-PSS) is dissolved in water-isopropanol
(IPA) mixed solvent, so as to be prepared for hole transmission layer solution (the PEDOT-PSS mass % of concentration 1).
On the ito film 11b of conductive support 11, after being coated with the hole transmission layer solution by spin-coating method, lead to
Cross heating plate and carry out the dryings of 30 minutes with 120 DEG C, the hole transmission layer 16 (thickness 50nm) so as to film forming.
＜ photosensitive layers 13C formation ＞
On the hole transmission layer 16 formed, solvent is changed to gamma-butyrolacton, in addition, with opto-electronic conversion
The formation ＞ identical methods of ＜ photosensitive layers 13A in the manufacture of element (specimen coding 101), there is provided include CH3NH3PbI3
Perovskite compound photosensitive layer 13C formation (thickness 200nm).So the 1st electrode 1E is made.
＜ compound layers 5B formation ＞
Then, on the 1st electrode 1E surface, (it is coated with 30 seconds) painting compound AC-15's by spin-coating method with 3000rpm
After 0.1 mass % aqueous isopropanols, by heating plate with 100 DEG C to the drying for the solution progress 30 minutes being coated with.So
Form compound layer 5B.
Here, the coating weight of aqueous isopropanol and the painting of the compound AC-1 of embodiment 1 0.1 mass % aqueous isopropanols
Cloth amount is identical.Also, confirm to be coated with the 1st electrode 1E's of the aqueous isopropanol containing compound AC-15 as described above
Surface, as a result, photosensitive layer 13C surface has compound AC-15.
The formation ＞ of ＜ electron transfer layers 4
Then, on the 1st electrode 1E surface, coating PC (is coated with 60 seconds) with 1500rpm by spin-coating method61BM chlorobenzene is molten
Liquid (PC61The BM mass % of concentration 1), so as to form electron transfer layer 4 (thickness 50nm).
The making ＞ of the electrodes 2 of ＜ the 2nd
By vapour deposition method, AM aluminum metallization has made the 2nd electrode 2 (thickness 100nm) on electron transfer layer 4.
So photo-electric conversion element 10E (specimen coding 401) is manufactured.
(manufacture of photo-electric conversion element (specimen coding c41))
In the manufacture of photo-electric conversion element (specimen coding 401), the aqueous isopropanol containing compound AC-15 is not coated with
In the 1st electrode 1E surface, in addition, to be manufactured with the manufacture identical method of photo-electric conversion element (specimen coding 401)
It is used for the photo-electric conversion element (specimen coding c41) compared.
The evaluation ＞ of ＜ durability
It is resistance to the ＜ of embodiment 1 respectively to the photo-electric conversion element (10 measured bodies) of each specimen coding so manufactured
The evaluation ＞ of long property similarly have rated durability.Show the result in table 4.
[table 4]
It is clear that, perovskite compound is used as in the photo-electric conversion element of light absorber, even if setting from the result of table 4
To sequentially form hole transmission layer 16, photosensitive layer 13C, compound layer 5B, electron transfer layer 4 and in conductive support 11
The structure of 2 electrodes 2, also shows that sufficient durability.
On the other hand, do not have the durability of specific compound AC photo-electric conversion element on the surface of the 1st electrode not
Fully.
Embodiment 5
(manufacture of photo-electric conversion element (specimen coding 501))
According to step described below, the photo-electric conversion element for not possessing hole transmission layer has been manufactured (with reference to shown in figure 6
Photo-electric conversion element 10F).
In the manufacture of photo-electric conversion element (specimen coding 112), hole transmission layer 3A is not provided with, but (change in the 1st electrode
Compound layer 5) on be provided with the 2nd electrode 2, in addition, with the manufacture identical side with photo-electric conversion element (specimen coding 112)
Method has manufactured the photo-electric conversion element (specimen coding 501) of the present invention.
Formed after compound layer, it is thus identified that compound AC-15 be present on the surface of the 1st electrode.
(manufacture of photo-electric conversion element (specimen coding c51))
In the manufacture of photo-electric conversion element (specimen coding 501), the aqueous isopropanol containing compound AC-15 is not coated with
In the 1st electrode 1F surface, in addition, to be manufactured with the manufacture identical method of photo-electric conversion element (specimen coding 501)
It is used for the photo-electric conversion element (specimen coding c51) compared.
The evaluation ＞ of ＜ durability
Respectively by the photo-electric conversion element (10 measured bodies) of each specimen coding so manufactured, in humidity 30RH%, temperature
20 hours are stood in the constant temperature and humidity container of 20 DEG C of degree, in addition, is commented in the same manner as the evaluation ＞ of the ＜ durability of embodiment 1
Valency durability.Show the result in table 5.
[table 5]
It is clear that, perovskite compound is used as in the photo-electric conversion element of light absorber, even if not from the result of table 5
Hole transmission layer is set, also shows that sufficient durability.
On the other hand, do not have the durability of specific compound AC photo-electric conversion element on the surface of the 1st electrode not
Fully.
As more than, even the photo-electric conversion element that perovskite compound is used as to light absorber is learnt, if in the 1st electrode
Surface set compound AC (compound layer), then excellent durability is shown.
Together the present invention is described with embodiments thereof, but unless specifically stated otherwise, then not in any of explanation
Details limits the present invention, it is believed that wide on the premise of the spirit and scope that should be shown in the claim for not violating institute's apposition
General explanation.
The application advocates to carry out the excellent of the patent application 2015-046440 of patent application in Japan based on March 9th, 2015
First weigh, herein with reference to the patent application, introduced using its content as a part for the record of this specification.
Symbol description
The electrodes of 1A~1F- the 1st, 11- conductive supports, 11a- supporting masses, 11b- transparency electrodes, 12- porous layers, 13A
~13C- photosensitive layers, 14- barrier layers, the electrodes of 2- the 2nd, 3A, 3B, 16- hole transmission layer, 4,15- electron transfer layers, 5A~5C-
Compound layer, 6- external circuits (lead), 10A~10F- photo-electric conversion elements, 100A~100F- are using solar cell
System, M- electro-motors.
Claims (12)
1. a kind of photo-electric conversion element, it is with the 1st electricity with the photosensitive layer comprising light absorber in conductive support
Pole and the 2nd electrode with the 1st electrode contraposition, wherein,
The light absorber, which includes, possesses the cation with periodic table first family element or cationic organic group A, institute
State the cation and anionic property atom or atomic group X anion of metallic atom M beyond periodic table first family element
The compound of perovskite type crystal structure,
There is the compound represented with following formula (AC) on the surface of the 1st electrode,
[chemical formula 1]
In formula, ring AACRepresent heterocycle；Z represents sulphur atom or oxygen atom；nZRepresent more than 1 integer；A represents ＞ C=CRY1RY2、
＞ C=S, ＞ C=O or ＞ C=NRY3；RY1And RY2Separately represent substituent；RY3Represent hydrogen atom or substituent；nATable
Show more than 0 integer；RACRepresent substituent；nRRepresent more than 0 integer；Wherein, Z is sulphur atom and nZFor 1 when, nRRepresent 1 with
On integer.
2. photo-electric conversion element according to claim 1, wherein,
The RACFor halogen atom, carbon number more than 5 alkyl or with halogen atom group.
3. photo-electric conversion element according to claim 1 or 2, wherein,
The ring AACFor the heteroaromatic of 5 yuan of rings or 6 yuan of rings.
4. photo-electric conversion element according to any one of claim 1 to 3, wherein,
At least one of the Z is oxygen atom.
5. photo-electric conversion element according to any one of claim 1 to 4, wherein,
The ring AACFor furan nucleus.
6. photo-electric conversion element according to any one of claim 1 to 5, wherein,
The compound with perovskite type crystal structure is the compound represented with following formula (I),
Formula (I)：AaMmXx
In formula, A represents periodic table first family element or the cationic organic group represented with following formula (1)；M represents the week
Metallic atom beyond phase table first family element；X represents anionic property atom or atomic group；A represents 1 or 2, m expression 1, a, m
And x meets a+2m=x；
Formula (1)：R1a-NH3
In formula, R1aRepresent substituent.
7. photo-electric conversion element according to claim 6, wherein,
The R1aFor alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl or the group that can be represented with following formula (2),
[chemical formula 2]
In formula, XaRepresent NR1c, oxygen atom or sulphur atom；R1bAnd R1cSeparately represent hydrogen atom or substituent；* * are represented
With being bonded for the nitrogen-atoms of formula (1).
8. photo-electric conversion element according to any one of claim 1 to 7, wherein,
The metallic atom is at least one kind of metallic atom in the group comprising lead and tin.
9. photo-electric conversion element according to any one of claim 1 to 8, wherein,
There is hole transmission layer between the 1st electrode and the 2nd electrode.
10. photo-electric conversion element according to any one of claim 1 to 9, wherein,
There is porous layer between the conductive support and the photosensitive layer.
11. a kind of solar cell, the photo-electric conversion element any one of its usage right requirement 1 to 10.
12. a kind of manufacture method of photo-electric conversion element, wherein,
Make in conductive support with comprising the sun with periodic table first family element or cationic organic group A from
The cation and anionic property atom of metallic atom M beyond sub, described periodic table first family element or atomic group X it is cloudy from
The compound of the perovskite type crystal structure of son is as the 1st electrode of the photosensitive layer of light absorber and containing with following formula (AC) table
The liquid contact for the compound shown,
[chemical formula 3]
In formula, ring AACRepresent heterocycle；Z represents sulphur atom or oxygen atom；nZRepresent more than 1 integer；A represents ＞ C=CRY1RY2、
＞ C=S, ＞ C=O or ＞ C=NRY3；RY1And RY2Separately represent substituent；RY3Represent hydrogen atom or substituent；nATable
Show more than 0 integer；RACRepresent substituent；nRRepresent more than 0 integer；Wherein, Z is sulphur atom and nZFor 1 when, nRRepresent 1 with
On integer.
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| PCT/JP2016/055236 WO2016143506A1 (en) | 2015-03-09 | 2016-02-23 | Photoelectric conversion element, solar cell, and method for producing photoelectric conversion element |
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| WO2018207857A1 (en) * | 2017-05-10 | 2018-11-15 | 国立大学法人 東京大学 | Organic-inorganic hybrid material and perovskite solar cell using same |
| JP2018195768A (en) * | 2017-05-19 | 2018-12-06 | 富士フイルム株式会社 | Photoelectric conversion element, solar battery, method for manufacturing photoelectric conversion element, and composition for photoelectric conversion element |
| KR20190078493A (en) | 2017-12-26 | 2019-07-04 | 주식회사 엘지화학 | Precursor for light absorbing layer, method for manufacturing the organic-inorganic complex solar cell using thereof, and organic-inorganic complex solar cell |
| US10727428B1 (en) * | 2019-02-01 | 2020-07-28 | Natioinal Technology & Engineering Solutions Of Sa | Organic-semiconducting hybrid solar cell |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6413009B2 (en) | 2018-10-31 |
| JPWO2016143506A1 (en) | 2018-01-25 |
| US20170372847A1 (en) | 2017-12-28 |
| KR20170121227A (en) | 2017-11-01 |
| EP3270431A4 (en) | 2018-01-17 |
| WO2016143506A1 (en) | 2016-09-15 |
| EP3270431A1 (en) | 2018-01-17 |
| CN107431130B (en) | 2020-05-22 |
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